Elongated phosphoranes by C-C coupling of haloaroylmethylidene-triphenylphosphoranes: Synthesis and applications

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Elongated phosphoranes by C–C coupling of haloaroylmethylidene-

triphenylphosphoranes: synthesis and applications

Thies Thiemann,*^aKuniharu Umeno,^bJian Wang,^bYumiko Tabuchi,^cKazuya Arima,^b

Masataka Watanabe,^bYasuko Tanaka,^aHideki Gorohmaru†^band Shuntaro Mataka^a

1

^aInstitute of Advanced Material Study, Kyushu University, 6-1, Kasuga-koh-en, Kasuga-shi,

Fukuoka 816-8580, Japan

^bGraduate School of Engineering, Kyushu University, 6-1, Kasuga-koh-en, Kasuga-shi,

Fukuoka 816-8580, Japan

^cFaculty of Engineering, Kyushu University, Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan

Received (in Cambridge, UK) 18th March 2002, Accepted 30th July 2002

First published as an Advance Article on the web 23rd August 2002

Haloaroylmethylidenephosphoranes 3 can be subjected to Pd() mediated C–C coupling reactions to yield diaryl-,

arylhetaryl-, dihetaryl, arylethenylaryl/hetaryl- and arylethynylaryl/hetaryl-carbonylmethylidenephosphoranes 4–9.

Suzuki–Kumada reactions can also be run in a one-step procedure from (haloaroylmethyl)triphenylphosphonium

bromides 2. Compounds 4–9 are air-stable phosphoranes which undergo formal Wittig-oleﬁnation reactions with

aldehydes 10 under benzoic acid catalysis. C–C coupling reaction and Wittig oleﬁnation can also be performed in a

one-step procedure. Preliminary experiments have been performed to carry out the synthesis on a solid support.

Applications to the chain elongation and functionalisation of the chain terminus in a C-7 substituted estra-1,3,5(10)-

triene 14 and a C-16 substituted estra-1,3,5(10),6-tetraene 12 are shown.

phenylphosphonium halides 2,⁵which in turn can be converted

Introduction

to the phosphoranes 3 by base-catalysed dehydrohalogenation

The Wittig oleﬁnation is a well-established reaction.¹After its

(usually by employing an aq. Na₂CO₃solution).⁹For the most

discovery²in 1949–1954³it developed very quickly into an

important implement in the tool-kit of the organic synthetic

part the haloaryl halomethyl ketones 1 are commercially avail-

able. Where they are not, the haloaryl methyl ketones were

chemist. The preparations of phosphoranes as reagents for the

brominated with bromine in acetic acid. The haloaryl methyl

Wittig oleﬁnation are manifold.⁴Early in the development of

ketones possess low solubility in acetic acid and it was found to

be very beneﬁcial to carry out the bromination of a suspension

new Wittig reagents interest focussed on phosphoranes in which

the ylene P᎐C bond is in conjugation with either a carbonyl⁵

᎐

of the starting material in acetic acid under ultrasonication.

or a cyano⁶group. These phosphoranes show little basicity,

The progress of the reaction could be monitored optically by

tolerate oxygen and can usually be stored as solids over a

the disappearance of color, ending in many cases with totally

long period of time. Furthermore, they discriminate between

colorless material which could be ﬁltered and used without any

further puriﬁcation.

carbaldehydes and ketones, reacting readily with aldehydes,

but only with very reactive ketones.⁷In the following the syn-

thesis, physical properties and reactivity in Wittig-oleﬁnation

a. C–C bond formation under Suzuki–Kumada conditions.

The aroylmethylidenephosphoranes are known to exhibit a

reactions of these phosphoranes are discussed.⁸

certain stability in slightly basic media. It is for this reason that

it was deemed possible to transform the haloaroylmethyl-

idenephosphoranes into aryl/hetarylaroylphosphoranes, when

Results and discussion

I. Synthesis

using the mild reaction conditions of the Suzuki–Kumada

cross-coupling reaction.^13,14The haloaroylmethylidenephos-

phoranes undergo the coupling reaction with a number of aryl-

boronic acids, upon using [Pd(PPh₃)₄, 2 M aq. Na₂CO₃, DME],

[Pd(PPh₃)₄, CsF, DME] or [K₃PO₄–DMF] (Tables 1 and 2).^15,16

Most of the arylboronic acids are commercially available, 4m–p

were prepared.^17,18

Haloaroylmethylidenetriphenylphosphoranes 3 (Scheme 1) are

easily synthesized by reacting haloaryl halomethyl ketones 1

with triphenylphosphine to yield the respective aroylmethyltri-

During the coupling reaction a small amount of phospho-

rane is hydrolysed to give the corresponding disubstituted

biphenyls and triphenylphosphine.¹⁹The amount of hydrolysed

phosphorane depends not only on the reaction time, but also

on the substituent(s) of the phosphorane, i.e. on the initially

used aryl/hetarylboronic acid. Thus, preliminary studies of

the electrochemical oxidation of the phosphoranes have also

shown that the electrochemical potential at which electrons are

transferred from the phosphoranes is dependent on the nature

of the substituent on the phenyl group. For the most part, a

linear relationship could be found between the oxidation poten-

tial at which the phosphorane is oxidized and the Hammett

Scheme 1 Synthesis of haloaroylmethylidenetriphenylphosphoranes.

† Corresponding author for the X-ray crystal structure.

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DOI: 10.1039/b202745n

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Table 1 Suzuki coupling of p-bromobenzoylmethylidenetriphenylphosphorane under various conditions

–Ar¹–Br

–Ar²

Variant^a

A

Yield (%)

64

–Ar¹–Br

–Ar²

Variant^a

A

Yield (%)

4a

60

90

4k

4l

A

B

C

A

89

62

65

4b

4c

B

36

98

4m

4n

D^b

A

91

89

A

85

16

4o

4p

A

68

66

4d

4e

A

—

94

4f/g^c

4h

A

55

65

4q

4r^d

A

70

58

4i

4j

^aA: Pd(PPh₃)₄, 2 M aq. Na₂CO₃, DME, 3–11 h, 75 ЊC; B: Pd(PPh₃)₄, CsF, DME, 3 h, 75 ЊC; C: Pd(Pd(PPh₃)₄, K₃PO₄, dry DMF, 4 h, 100 ЊC; D:

Pd(OAc)₂, NaHCO₃, Bu₄NCl, chloroform, 72 h, rt. Note: for methods B and C the corresponding boronic acid trimethylene glycol esters were used.

^bFor Suzuki-type coupling under PTC conditions, see ref. 22. ^cDenotes results for both 2,6-diﬂuorophenylboronic acid and pentaﬂuorophenyl-

boronic acid. ^dBis-coupling compound.

parameter of the benzoyl substituent.²⁰In certain cases, as for

thienylbenzoylmethylidenetriphenylphosphorane, this relation

is more complex, and does not follow the electron-donating/

electron-withdrawing character of the substituent.²⁰Never-

theless, the phosphoranes are by far the major products in the

Suzuki–Kumada coupling. They can be puriﬁed easily either

by precipitation or by column chromatography on silica gel

and subsequent recrystallization. The system [Pd(PPh₃)₄, CsF,

DME] gives slightly better yields in a number of cases. The

system [Na₂CO₃–DME] is environmentally more viable and

cheaper, and it was thus used most of all. It is possible to carry

out Suzuki–Kumada coupling reactions with haloaroylmethyl-

idenephosphoranes using phase-transfer conditions (PTC).

These conditions resemble the conditions used by Jeﬀery^21,22

(see below) in Heck reactions. Palladium acetate is used as the

Pd catalyst, NaHCO₃as the base and tetrabutylammonium

chloride as the phase-transfer catalyst. The reactions can be

carried out in chloroform. They are carried out at rt, however,

the reaction time tends to be long (72 h). At rt only the

iodoarylmethylidenephosphoranes give good results in the

Suzuki–Kumada coupling under PTC conditions.

Interestingly, both pentaﬂuoro- as well as 2,5-diﬂuorophenyl-

boronic acids do not undergo the coupling reaction under the

conditions tried. It may be that the boronic acids hydrolyse too

quickly in these cases—it is known that ﬂuoro substituents

accelerate the hydrolysis.²³On the other hand, both the p-

and the o-monoﬂuorophenylboronic acids give the coupling

products in acceptable yields.

As the aroylmethylidenephosphoranes themselves are pre-

pared under base-induced elimination of ‘HBr’ from the

corresponding aroyltriphenylphosphonium bromides, it only

seemed expedient to subject the aroyltriphenylphosphonium

bromides themselves to the C–C bond-forming reaction under

Suzuki–Kumada conditions. Indeed, when this reaction was

carried out, the phosphoranes 4 could be isolated in good yield

(Table 3). Here, elimination to the phosphoranes and the C–C

bond-forming reaction take place as a one-pot procedure.

As the phosphonium salts are somewhat more stable than the

J. Chem. Soc., Perkin Trans. 1, 2002, 2090–2110

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Table 2 Suzuki coupling of haloaroylmethylidenetriphenylphosphoranes

–Ar¹–Br

–Ar²

Yield (%)

62

–Ar¹–Br

–Ar²

Yield (%)

89

5a

3b

5m

6a

94

3b

72

57

78

5b

5c

5d

3c

65

95

55

6b

6c

6d

3b

78

5e

3b

95

55

66

5f

3c

72

55

81

6e

6f

5g

5h

7a

3b

49

5i

3d

95

82

7b

7c

3b

75

56

5j

5k

3d

89

70

7d

7e

3b

13

5l

corresponding phosphoranes and can be stored over long

periods of time, the use of the phosphonium salts as starting

materials in the coupling reactions is a viable alternative to the

reactions presented above.

species. While Jeﬀery²¹uses tetrabutylammonium chloride as

phase-transfer catalyst, other ammonium salts serve equally

well. In our case benzyltrimethylammonium chloride was used.

Although the reaction is run at rt, the reaction time tends to be

long. Not all the reactions have been monitored with respect to

reaction time, however, as an example, the reaction between 3e

and acrylonitrile is not complete after 42 h. After 60 h most

of the systems tried show virtually no more starting material.

Exceptions are methyl vinyl ketone and vinylpyridine. Vinyl-

pyridine could not be reacted under these conditions. Methyl

vinyl ketone could be reacted; the products, however, could not

be isolated (Table 4).

Interestingly, under the same conditions the reaction of

p-bromobenzoylmethylidenetriphenylphosphorane (3a) with

acrylonitrile does not proceed and the reaction under Jeﬀery

conditions seems to be limited to an iodo-substituted coupling

partner.

b. C–C bond formation under Heck conditions. Although

the Heck reaction is a well-studied transformation in organic

chemistry, to our knowledge no example of a Heck reaction

with phosphoranes to yield substituted phosphoranes²⁴has

been described in the literature.

Here, we have subjected both the p-bromobenzoylmethyli-

denetriphenylphosphorane (3a) and the corresponding iodo-

substituted 3e to Heck reactions under a number of conditions.

Under the classical conditions, 3a gives the Heck reaction

products, e.g. 8a–c in only mediocre yields. Better yields are

achieved using conditions employed formerly by Jeﬀery. In this

case the reaction is run in a-two phase system (solid–liquid)

with a tetraalkylammonium salt as phase-transfer catalyst. The

reaction is run at rt and no triphenylphosphine is added as

ligand, which would help stabilize the transient palladium()

c. C–C bond formation by Pd(0)-catalysed ethynylation.

p-Iodophenylcarbonylmethylidenetriphenylphosphorane (3e)

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Table

3

Suzuki coupling of haloaroylmethylidenetriphenylphos-

was successfully reacted with substituted phenylacetylenes and

phoranes

thienylacetylene. The p-substituted phenylacetylenes them-

selves were prepared in the usual manner by reaction of the

p-substituted bromoarenes with trimethylsilylacetylene [(Ph₃-

P)₂PdCl₂, CuI, i-Pr₂NH, toluene] with subsequent desilylation

(1 M KOH, MeOH). p-Ethynylbenzamide was obtained by

partial hydrolysis of p-ethynylbenzonitrile [(n-C₄H₉)N^ϩHSO₄

,

Ϫ

30 w% aq. H₂O₂, CH₂Cl₂–20 w% aq. NaOH, 20–25 ЊC, PTC

conditions).²⁵The ethynylation reactions of the p-iodobenzoyl-

methylidenetriphenylphosphorane (3e) itself were carried out

with the typical Pd(PPh₃)₄–CuI catalyst system in toluene (see

Table 5). The yields of the reactions were found to be dependent

on the p-substituent of the phenylacetylene. Thus, while in the

reaction of p-nitrophenylacetylene the coupling product 9c

could be obtained in an almost quantitative yield, the corre-

sponding p-amido-substituted product 9d was only obtained in

a mediocre yield. The outcome with certain substrates, such as

with the thienyl derivative 9e or with p-cyanophenylacetylene,

product 9b, was found to be strongly dependent on the reaction

time. Thus, p-cyanophenylacetylene gave the product in 98%

yield after 3 h, while 9b was only obtained in 50% yield after

13 h.

Yield (%)^a

from

phosphorane

–Ar¹–Br

–Ar²

Yield (%)

64 (4b)

65

49 (4a)

62 (4d)

74 (4e)

64

68

66

II. Properties

a. Spectroscopic data. The carbon NMR spectra of all the

conjugated phosphoranes that have been prepared by Suzuki

coupling show the methylidene ylide carbon at about δ 50

ppm.^26,27The value of the chemical shift of this carbon is not

aﬀected greatly by the substituent on the benzoyl or thienoyl

units. The UV spectra of compounds 3a, 4a, 4n, 5b, 5c, 5h, and

5m were taken. The samples were measured at a concentration

of 2 × 10^Ϫ5M in 99.5% ethanol (0.5% H₂O) and in CH₂Cl₂.

In the latter series, a number of single ‘core’ benzoylmethyl-

idenetriphosphoranes were also included. In general, the

coupled products, e.g. 4a and 4n, show a bathochromic shift

and a hyperchromic eﬀect. The thienoylmethylidenephos-

42 (4j)

54 (4k)

55 (4l)

58

60

90

^aThese yields are given for comparison. Partly, they can also be found

in Table 1.

Table 4 Cross-coupling of phosphoranes with vinylic compounds (Heck conditions)

–Ar¹–X

–EWG

Variant^a

A

Yield (%)

45

–Ar¹–X

–EWG

Variant^a

A

Yield (%)

6

8a

B^b

A

75

25

8a

8b

3a

A

18

38

—

8b

8c

3e

C

A

55

—

8b

3e

3a

A

—

A

—

C

64

96

8d

8c

3e

^aA: PPh₃, Et₃N, DMF, 15–24 h, 100 ЊC; B: NaHCO₃, Bu₄NCl, chloroform; 72 h, rt; C: NaHCO₃, [PhCH₂N(CH₃)₃]Cl, chloroform, 40–60 h, rt. ^bFor

Heck reaction under PTC conditions, also see ref. 21.

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Fig. 1 Representation of the X-ray crystal structure of 4-(2Ј-naphthyl)benzoylmethylidenetriphenylphosphorane.

Table 5 Cross-coupling of phosphoranes with arylacetylenes

electrocyclovoltammetry, the compounds show no reduction

peak typical for a carbonyl group.²⁰

b. Structural properties. A single-crystal X-ray structural

analysis was carried out with compound 4l (Fig. 1). The X-ray

crystal structure of benzoylmethylidenetriphenylphosphorane

is known in the literature.²⁸In 4l the bond length P1–C18 is

1.726 Å. This is slightly longer than the bond in benzoylmethyl-

idenetriphenylphosphorane itself at 1.71 Å. As the value for the

bond length of a typical PC double bond is taken to be around

1.67 Å and that of a typical PC single bond to be around

1.87 Å, the bond in 4l has more character of a PC double

bond rather than a PC single bond. However, the single bond

character increases slightly with the added aryl group. The

X-ray study of 4l also reveals that the naphtho group is not

in conjugation with the phenylene unit. This, however, is most

likely due to better packing in the crystal. The dihedral angle

C1–C2–C11–C16 measures 129.9Њ.

–Ar¹–X

–Ar²

Yield (%)

4

Time/h

13

9a

9b

3e

5

13

9

9b

9c

3

3e

13

c. Cytotoxic behavior. Compounds 4a, 4e, 4h, 4j, 5b, 5c, 5m,

and 7d were subjected to a three-cell line (NCI-H460 [Lung],

MCF7 [Breast], SF-268 [CNS]), one-dose anticancer assay.²⁹Of

these compounds only 5b and 5c were found to be inactive.

Compounds 4a, 4e, 4h, 4j, 5m, and 7d were then subjected to

an in vitro anti-tumour screen comprising 60 human tumour

cell lines. The compounds showed moderate but not selective

activity towards a number of cancer cell types. As there is a

slow hydrolysis of the compounds in slightly acidic aqueous

media, it still needed to be ascertained what role the hydrolysis

products, e.g., the acetyl-substituted biaryls, play in the cyto-

toxicity of the phosphoranes. Acetyl-substituted biaryls have

been known to have physiological activity, but have been

patented mainly in the area of blood anti-coagulents. Initial

electroanalytical experiments on the oxidizability of the phos-

phoranes, however, do not show any relationship between the

sensitivity of the phosphoranes towards oxidation and their

cytotoxic activity.

13

46

9d

9e

13

4

phoranes show a shift of the absorption maximum to longer

wavelengths when compared to the corresponding benzoyl-

methylidenephosphoranes, e.g. 5b vs. 4a. Typical absorption

maxima (λ_max[solvent]/nm, log ε) are as follows: 3a (322_[EtOH], 4.05);

4a (328_[EtOH], 4.30); 4n (342_[EtOH], 4.45); 5b (356_[EtOH], 4.44); 5c

(350_[EtOH], 4.37); 5h (357_[EtOH], 4.15); 5m (353_[EtOH], 4.33).

As in the case of the unsubstituted benzoylmethyl-

idenetriphenylphosphorane, the elongated phosphoranes

reported here can be best described in terms of their structure

as being ylides (rather than ylenes). This can be seen from their

UV spectra, their ¹³C NMR spectra (vide supra), and the X-ray

crystal structure of 4l (vide infra). Also, when analysed by

III. Wittig-oleﬁnation reaction of the phosphoranes

For the most part, conjugated phosphoranes such as those

described above are quite unreactive towards ketones. Few

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Scheme 2 Acid-catalysed Wittig oleﬁnation of estrone derivatives with elongated phosphoranes.

Table 6 Acid-catalysed Wittig oleﬁnation with elongated phospho-

ranes

examples of ketones are known that are suﬃciently reactive for

the oleﬁnation reaction with the phosphoranes to proceed.^30,31

Aldehydes, however, readily react with the phosphoranes.

Here, both arenecarbaldehyde (p-tolualdehyde and m-nitro-

benzaldehyde) as well as alkanecarbaldehydes (n-butanal) have

been used as the aldehyde component. Two steroidal substrates,

12³²and 14, have also been used. Both are estranes, one (12)³²

with a formyl substituent at C-16, the other (14) with a formyl

group as the terminal functionality of a chain substituting the

estrane at C-7α. The latter has been synthesized as an inter-

mediate to C-7α-substituted estra-1,3,5(10)-trienes and to C-7-

substituted estra-1,3,5(10),6-tetraenes^33–35as novel ligands for

the estrogen receptor ERα. This research is closely connected

to the development of radiodiagnostics and of drug delivery

systems for estrogen-positive breast cancer.^33–36

All of the substrates could be reacted with the elongated

phosphoranes used, as shown in Table 6 and in Scheme 2. It

has been found that it is advantageous to carry out the Wittig

reactions under acid catalysis.^37,38Here, benzoic acid has been

used. The major products obtained and those isolated are (E)-

isomers.

RCHO

–Ar²

Yield (%)

98

11a

In our endeavour to develop one-pot procedures, which are

more time- and cost-eﬀective while limiting excessive produc-

tion of waste materials, we looked at the possibility of running

the Suzuki–Kumada coupling concurrently with the Wittig

oleﬁnation.³¹Here, the products were obtained in good yields

(Scheme 3). It must be pointed out that two equivalents of

arylboronic acid were used. Where the carbaldehyde substrates

also carried an interchangeable halo functionality a mixture

of products was obtained, as the Suzuki–Kumada coupling

also took place on the carbaldehyde component to give doubly-

coupled products. The separation of products such as these

is diﬃcult to achieve. Where product mixtures are obtained it is

often advisable to follow the step-wise sequence to facilitate

work-up.

10a

98

90

97

11b

11c

11d

11e

50

45

11f

IV. Synthesis on solid support³⁹

Wittig oleﬁnations using phosphoranes derived from triphenyl-

phosphine-polystyrene have been described in the literature. The

preparation of the individual phosphoranes varies depending

10a

11g

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Scheme 3 Suzuki coupling–Wittig oleﬁnation as a one-pot/three-component reaction.

Scheme 4 Phosphorane synthesis and Wittig reaction were carried out successfully with a number of boronic acids on a solid support [(p-

styryldiphenylphosphine) polymer]. The problems of eﬃcient recycling of the ensuing phosphine oxide polymer and cleansing of the polymer from

palladium after the coupling reactions still need to be solved.

on the nature and the stability of phosphorane synthesized

(Scheme 4). In the case described here, the corresponding halo-

substituted α-bromoacetoarenone, such as p-bromophenacyl

bromide, could be reacted with p-poly(styryldiphenylphos-

phine)⁴⁰in DME (65 ЊC, 20 h). The ensuing phosphonium

bromide was dehydrobrominated to the phosphorane using

either aq. 7 w% Na₂CO₃(1 h, rt) or sodium hexamethyldi-

silazane in THF (4 h, rt). While for the preparation of poly-

(p-bromobenzoylmethylidenediphenylstyrylphosphine) either

Na₂CO₃or preferably sodium hexamethyldisilazane could be

used, the synthesis of the bromothienyl analog did not proceed

with sodium hexadimethyldisilazane.

arylboronic acids. Again, for the thienoylmethylidenephospho-

ranes, the reaction conditions [Pd(PPh₃)₄, aq. Na₂CO₃, DME]

were diﬀerent from those used for the bromobenzoylphospho-

rane [Pd(PPh₃)₄, CsF, DME] and gave better results.

The resulting phosphoranes were reacted with p-tolualde-

hyde (10a) in reﬂuxing benzene in the presence of a catalytic

amount of benzoic acid. The resulting alkene leaves the solid

support, with triphenylphosphine oxide remaining on the

support. The reaction mixture was analysed after termination

1

of the reaction by H NMR spectroscopy. Thereafter, it was

separated by column chromatography or by preparative thin

layer chromatography and the coupled phosphoranes were

isolated as pure substances.

The phosphoranes bound to the solid support were subjected

to Suzuki–Kumada coupling⁴¹reactions with a number of

Reactions were also carried out with 17-bromo-16-formyl-

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Scheme 5

3-methoxyestra-1,3,5(10),16-tetraene (12). Representative

reactions are shown in Scheme 5.

have been carried out to recycle the solid support reagent as

triphenylphosphine-polystyrene, which entails a reduction step

of triphenylphosphine oxide to triphenylphosphine. An added

diﬃculty in the recycling process comes from the fact that

the Suzuki coupling leaves palladium adsorbed to the solid

support. A number of methods are known for the reduction of

triphenylphosphine oxide to triphenylphosphine. Thus, mono-

meric triphenylphosphine oxide in solution can be reduced by

LiAlH₄–CeCl₃,^42aby trichlorosilane (Cl₃SiH)^42bas well as with

a hydrocarbon/carbon reductant^42cat high temperatures. Here,

preliminary experiments have been carried out with LiAlH₄–

CeCl₃. For this experiment triphenylphosphine-polystyrene was

treated with MCPBA and oxidized to triphenylphosphine oxide

polystyrene. With this in hand, it could be shown both by IR

spectrocopy of the product and by repeating the ﬁrst step

(preparation of the phosphonium salt) of the sequence

described above that LiAlH₄–CeCl₃also reduces polymer-

bound triphenylphosphine oxide. However, the purity of the

reduced product obtained still needs to be improved.

After each synthetic step on the support, the support was

analysed by IR spectroscopy. Very clear and signiﬁcant changes

in the IR bands could be observed after every step and within

the ‘ﬁnger-print’ region a clear identiﬁcation of the polymer-

bound phosphoranes could be made, as the absorption frequen-

cies closely resembled those of the monomeric phosphoranes

synthesized in solution and isolated in substance: polymer-

bound phosphorane vs. monomeric phosphorane [p-biphenyl-

carbonylmethylidenetriphenylphosphorane (4b), measured as

KBr pellets] 1564 (1567), 1491 (1481), 1437 (1436), 1384 (1388),

1109 (1102), 884 (880), 749 (746), 687 (693) cm^Ϫ1

.

Elemental analyses were carried out after every step for repre-

sentative samples. The elemental analysis of the commercial

triphenylphosphine-polystyrene showed the loading of the

phosphine to be 1.6 mmol g^Ϫ1reagent. Analyses of the support/

supported material after the preparation of the phosphonium

bromide, which includes a thorough washing of the solid sup-

port with THF and dichloromethane at the end of the reaction,

showed this ﬁrst step to be a very clean reaction. The second

step, which is the actual preparation of the phosphorane that is

to be elongated subsequently by C–C coupling and consists of

the dehydrobromination of the corresponding phosphonium

salt, leaves impurities on the solid support, probably due to

salt inclusion. Diﬀerent methods of washing the support after

the reaction were tested at this stage: a) rinsing with water at rt;

b) washing with hot water (50 ЊC), c) treating the support with

water under sonication in an Kaijo Denki Cleaning Bath 100

(for 1 h at rt). Good results were obtained with method c);

in certain cases the results achieved by method a) were

comparable.

Experimental

General

Melting points were measured on a Yanaco microscopic hot-

stage and are uncorrected. Infrared spectra were measured with

JASCO IR-700 and Nippon Denshi JIR-AQ2OM machines.

¹H and ¹³C NMR spectra were recorded with a JEOL EX-270

spectrometer. The chemical shifts are relative to TMS (solvent

CDCl₃, unless otherwise noted). Mass spectra were measured

with a JMS-01-SG-2 spectrometer (EI, 70 eV). Column chro-

matography was carried out on Wakogel 300. All experiments

were purged with argon at the start. Ether = diethyl ether.

Commercially available triphenylphosphine-polystyrene

After the Wittig reaction, an appreciable amount of phos-

phine oxide is formed on the solid support. Initial experiments

J. Chem. Soc., Perkin Trans. 1, 2002, 2090–2110

2097

View Article Online

(100–200 mesh, loading: 1.2 mmol triphenylphosphine g^Ϫ1

reagent, Novabiochem) was used. The preparative procedures

for 17-bromo-16-formyl-3-methoxyestra-1,3,5(10),16-tetraene

(12) and 14 have been described earlier.

The preparations of 4-(m-nitrophenyl)benzoylmethylidenetri-

phenylphosphorane 4h from 3a, of 4-(2Ј,4Ј-diﬂuorophenyl)-

benzoylmethylidenetriphenylphosphorane 4e from 2a, and of

1-(p-phenylbenzoyl)-2-(p-tolyl)ethene 11a by Wittig oleﬁnation

from 4b and 10a have been reported previously.

dimethoxyethane (DME) (5 mL) and 2 M aq. Na₂CO₃(3.7 mL)

was heated at 75 ЊC for 5 h. Thereafter the cooled solution was

diluted with water (10 mL) and extracted with ether (10 mL)

and chloroform (2 × 15 mL). The combined organic phase

was washed with water, dried over MgSO₄and concentrated

in vacuo. Addition of ether (15 mL) to the residue led to preci-

pitation of 4a (304 mg, 64%) as a colorless powder, mp 231 ЊC

(ether) (Found: C, 81.50; H, 5.66. C₃₃H₂₇O₂P requires C, 81.46;

H, 5.59%). ν_max(KBr)/cm^Ϫ13050, 1604, 1580, 1563, 1505, 1481,

1438, 1384, 1253, 1181, 1103, 882, 837, 744, 717, 690; δ_H(270

MHz, CDCl₃) 3.84 (3H, s, OCH₃), 4.47 (1H, d, ²J_H–P24.4 Hz),

6.97 (2H, d, ³J 8.9 Hz), 8.02 (2H, d, ³J 8.2 Hz); δ_C(67.8 MHz,

CDCl₃, DEPT 90, DEPT 135) 50.65 (CH, ¹J_C᎐P112 Hz), 55.34,

114.14 (CH), 126.02 (CH), 127.10 (C_quat, J_C–P^᎐91.5 Hz), 127.40

(CH), 128.16 (CH), 128.87 (CH, J_C–P12.2 Hz), 132.04 (CH, J_C–P

o-Bromophenylcarbonylmethylidenetriphenylphosphorane (3c)

To a stirred solution of triphenylphosphine (2.19 g, 8.35 mmol)

in chloroform (5 mL) was added dropwise (o-bromo)bromo-

acetylbenzene (2.11 g, 7.50 mmol) in chloroform (5 mL). The

solution, which warmed slightly upon addition, was stirred at

rt for 10 h. Thereafter the mixture was poured into dry ether

(100 mL) and ﬁltered. The ﬁlter cake, which is hygroscopic,

was transferred quickly into a mixture of 10 w% aq. Na₂CO₃

(30 mL) and CH₂Cl₂(10 mL). The resulting two-phase solution

was stirred at rt for 10 h. Thereafter, the organic phase was

separated and the aqueous phase was extracted with CH₂Cl₂

(3 × 15 mL). The organic phase was dried over anhydrous

MgSO₄and concentrated in vacuo. The residue was subjected to

column chromatography on silica gel (ether) to give 3c (1.0 g,

29%) as colorless plates, mp 175–176 ЊC (Found: C, 68.06; H,

4.38. C₂₆H₂₀BrOP requires C, 67.99; H, 4.39%). ν_max(KBr)/cm^Ϫ1

3050, 2920, 1530, 1392, 1108, 747, 717, 692, 520, 508; δ_H(270

2.4 Hz), 133.17 (CH, J_C–P9.8 Hz), 133.55 (C_quat), 139.48 (C_quat

,

2

J_C–P14.6 Hz), 141.63 (C_quat), 159.17 (C_quat), 184.42 (C᎐O, J

᎐

C–P

3.6 Hz); MS (70 eV) m/z 486 (M^ϩ, 100%), 457 (M^ϩϪ CHO, 21),

303 ([M^ϩϪ p-MeO-Ph-Ph], 70); HRMS found: 486.1748;

calcd. for C₃₃H₂₇O₂P: 486.1749.

Method 2. A mixture of 3a (153 mg, 0.33 mmol), p-methoxy-

phenylboronic acid (100 mg, 0.66 mmol), caesium ﬂuoride

(200 mg, 1.32 mmol) and Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3mmol)

in DME (4 mL) was held at reﬂux for 3 h. The cooled solution

was diluted with water (10 mL) and extracted with chloroform

(3 × 10 mL). The organic phase was dried over anhydrous

MgSO₄and concentrated in vacuo. Column chromatography on

silica gel [eluant: ether ether–ethyl acetate (1 : 10)] gave 4a

(142 mg, 89%).

2

MHz, CDCl₃) 4.04 (1H, d, J_P–H24.7 Hz), 7.11 (1H, m), 7.26

(1H, m), 7.45–7.60 (11H, m), 7.72–7.81 (6H, m); δ_C(67.8 MHz,

CDCl₃, DEPT 90, DEPT 135) 54.93 (¹J_C᎐P104.9 Hz), 119.87

᎐

1

(C_quat), 126.56 (C_quat, J_C–P90.2 Hz), 126.74 (CH, 2C), 128.88

Method 3. A mixture of 3a (153 mg, 0.33 mmol), p-methoxy-

phenylboronic acid trimethyleneglycol ester (127 mg, 0.66

mmol), Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3mmol), dry K₃PO₄

(212 mg, 1.00 mmol) in dry DMF (5 mL) was held at 100 ЊC

for 4 h. Thereafter, the cooled mixture was poured into water

(75 mL) and extracted with chloroform (3 × 20 mL). The

combined organic phase was dried over anhydrous MgSO₄

and concentrated in vacuo. The residue was subjected to

column chromatography on silica gel (ether) to give 4a (100 mg,

62%).

(CH, J_C–P12.2 Hz), 129.24 (CH), 132.19 (CH, J_C–P3.6 Hz),

132.87 (CH), 133.22 (CH, 10.9 Hz), 145.43 (C_quat, J_C–P15.8 Hz),

186.76 (J_C–P3.7 Hz, C᎐O, C_quat); MS (FAB, 3-nitrobenzyl

᎐

alcohol) m/z 461 (⁸¹BrMH^ϩ, 100%), 459 (⁷⁹BrMH^ϩ, 100), 303

(47); MS (70 eV) m/z 460 (⁸¹BrM^ϩ, 50%), 458 (⁷⁹BrM^ϩ, 50);

HRMS found: 460.0403; calcd. for C₂₆H₂₀O⁸¹BrP: 460.0418;

found: 458.0439; calcd. for C₂₆H₂₀O⁷⁹BrP: 458.0435.

p-Iodophenylcarbonylmethylidenetriphenylphosphorane (3e)

(p-Bromoacetyl)iodobenzene (3.01 g, 9.26 mmol) and triphenyl-

phosphine (2.70 g, 10.31 mmol) in chloroform (15 mL) were

reacted as above to give hygroscopic p-iodobenzoylmethyl-

triphenylphosphonium bromide, which, after ﬁltration, was

immediately transferred to a second ﬂask where it was reacted

with aq. 10 w% Na₂CO₃(37 mL). After the reaction mixture

had been extracted with chloroform, dried and concentrated

in vacuo, the residue was subjected to column chromatography

on silica gel (ether ether–chloroform 1 : 1) to give 3e (1.88 g,

40%); R_f0.42 (ether); mp 217–218 ЊC (ether) (Found: C, 61.19;

H, 4.02. C₂₆H₂₀OPI requires C, 61.68; H, 3.98%). ν_max(KBr)/

cm^Ϫ13052, 1576, 1513, 1482, 1436, 1399, 1376, 1177, 1105,

1070, 1004, 885, 742, 691; δ_H(270 MHz, CDCl₃) 4.39 (1H, d,

²J_P–H23.8 Hz), 7.43–7.50 (6H, m), 7.54–7.58 (3H, m), 7.66–7.74

(10H, m); δ_C(67.8 MHz, CDCl₃, DEPT 90, DEPT 135) 51.20

Biphenyl-4-ylcarbonylmethylidenetriphenylphosphorane (4b)

Method A. A mixture of 3a (448 mg, 0.97 mmol), phenyl-

boronic acid (238 mg, 1.95 mmol), Pd(PPh₃)₄(27 mg, 2.3 ×

10^Ϫ2mmol) in DME (5 mL) and 2 M aq. Na₂CO₃(3.7 mL)

was reacted as above (procedure A). After concentration of

the organic phase in vacuo, the residue was subjected to

chromatography on silica gel (eluant ether) to give 4b (287 mg,

65%) as a colorless solid, mp 242–244 ЊC (ether) (Found: C,

84.31; H, 5.55. C₃₂H₂₅OP requires C, 84.19; H, 5.52%). ν_max

(KBr)/cm^Ϫ13028, 1567, 1509, 1481, 1436, 1408, 1388, 1102,

880, 746, 693; δ_H(270 MHz, CDCl₃) 2.40 (3H, s, CH₃), 3.87

(3H, s, OCH₃), 7.01 (2H, d, ³J 8.6 Hz), 7.24 (2H, d, ³J 9.2 Hz),

7.58–7.67 (6H, m), 7.69 (2H, d, ³J 8.2 Hz), 7.83 (1H, d, ³J 15.8

3

Hz), 8.09 (2H, d, J 8.2 Hz); δ_C(67.8 MHz, CDCl₃, DEPT 90,

1

(¹J_C᎐P112.1 Hz), 95.83 (C_quat), 126.73 (C_quat, J_C–P91.3 Hz),

1

᎐

DEPT 135) 50.82 (CH, J_C᎐P112 Hz), 126.44 (CH), 127.15

128.82 (CH), 128.91 (CH, J_C–P12.2 Hz), 132.16 (CH, J_C–P4.1

Hz), 133.10 (CH, J_C–P10.9 Hz), 136.80 (CH), 140.70 (C_quat, J_C–P

(CH), 127.27 (CH), 127.42 (CH), 128.27 (C_quat, J_C–P84 Hz),

128.74 (CH, J_C–P7.3 Hz), 132.03 (CH), 132.07 (CH), 133.17

(CH, J_C–P9.8 Hz), 140.07 (C_quat, J_C–P14.6 Hz), 141.00 (C_quat),

14.6 Hz), 183.60 (C_quat, J_C–P3.7 Hz, C᎐O); MS (FAB, 3-

᎐

nitrobenzyl alcohol) m/z 507 (MH^ϩ, 100%), 303 (28); HRMS

142.03 (C_quat), 184.35 (C᎐O, ²J_C–P3.6 Hz); MS (70 eV) m/z 456

᎐

found: 507.0374; calcd. for C₂₆H₂₁OPI: 507.0375 (MH^ϩ).

(M^ϩ, 100%), 303 (Ph₃PCHCO^ϩ, 72); HRMS found: 456.1640;

calcd. for C₃₂H₂₅OP: 456.1643.

4Ј-Methoxybiphenyl-4-ylcarbonylmethylidenetriphenylphos-

phorane (4a)—general procedure A

Method B (variant D). A mixture of 3a (108 mg, 0.21[5]

mmol), phenylboronic acid (53 mg, 0.43 mmol), NaHCO₃

(44 mg, 0.52 mmol), tetrabutylammonium chloride (71 mg,

0.25[5] mmol) and Pd(OAc)₂(12 mg, 5.3 × 10^Ϫ2mmol) in

chloroform (1.5 mL) was stirred for 72 h at rt. Thereafter water

Method 1. A mixture of p-bromobenzoylmethylidenephos-

phorane (3a) (448 mg, 0.97 mmol), p-methoxyphenyl-

boronic acid (297 mg, 1.95 mmol) and tetrakis(triphenylphos-

phine)palladium() (27 mg, 2.3

×

10^Ϫ2mmol) in 1,2-

2098 J. Chem. Soc., Perkin Trans. 1, 2002, 2090–2110

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(5 mL) was added and the mixture was extracted with chloro-

form (3 × 10 mL). The combined organic phase was washed

with water (2 × 5 mL), dried over anhydrous MgSO₄and con-

centrated in vacuo to give a residue, which was subjected to

column chromatography on silica gel (ether) to give 4b (88 mg,

91%).

162.89 (¹J_C–F166.3, ³J_C–F11.0 Hz), 184.25 (²J_C–P2.4 Hz, C᎐O);

᎐

MS (70 eV) m/z 492 (M^ϩ, 100%), 463 (19), 303 (Ph₃PCHCO^ϩ,

72). HRMS found: 492.1458; calcd. for C₃₂H₂₃OF₂P: 492.1455.

4-(p-Vinylphenyl)benzoylmethylidenetriphenylphosphorane (4i)

A mixture of 3a (153 mg, 0.33 mmol), 4-vinylphenylboronic

acid (97 mg, 0.66 mmol) and Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3

mmol) in DME (3 mL) and 2 M aq. Na₂CO₃(1.3 mL) was held

at 75 ЊC for 5 h. Work-up according to general procedure A and

column chromatography on silica gel (ether) gave 4i (111 mg,

70%) as a pale yellow solid, R_f0.29 (ether); mp 216–218 ЊC

(ether) (Found: C, 84.02; H, 5.82. C₃₄H₂₇OPؒ0.25H₂O requires

C, 83.84; H, 5.69%); ν_max(KBr)/cm^Ϫ11475, 1375, 1175, 1095,

880, 825, 740, 685; δ_H(270 MHz, CDCl₃) 4.46 (1H, br s), 5.26

(1H, d, ³J_cis10.8 Hz), 5.79 (1H, d, ²J_trans17.8 Hz), 6.75 (1H, dd,

³J_trans17.8, ³J_cis10.8 Hz), 7.46–7.77 (21H, m), 8.04 (2H, d, ³J 8.3

Hz); δ_CNMR (67.8 MHz, CDCl₃, DEPT 90, DEPT 135) 50.91

p-(m-Methoxyphenyl)benzoylmethylidenetriphenylphosphorane

(4c)

A mixture of 3a (263 mg, 0.57 mmol), m-methoxyphenyl-

boronic acid (148 mg, 0.97 mmol), Pd(PPh₃)₄(21 mg, 1.7 × 10^Ϫ2

mmol) in 2 M Na₂CO₃(2.3 mL) and DME (3.5 mL) was held at

reﬂux for 9 h. Thereafter the cooled reaction mixture was

worked up according to procedure A. Column chromatography

on silica gel (ether ethyl acetate–ether 1 : 9) gave 4c (246 mg,

89%) as a slightly yellow solid, mp 72–74 ЊC (ether); R_f0.17

(ether–ethyl acetate 1 : 9) (Found: C, 81.31; H, 5.68. C₃₃H₂₇O₂P

requires: C, 81.46; H, 5.59%); ν_max(KBr)/cm^Ϫ13052, 2956, 1602,

1569, 1511, 1403, 1383, 1106, 884, 692; δ_H(270 MHz, CDCl₃,

1

(CH, J_C᎐P112.3 Hz), 113.83 (Ϫ), 126.31 (CH), 126.59 (CH),

127.09 (C_quat, ¹J_C–P90.3 Hz), 127.22 (CH), 127.45 (CH), 128.89

(CH, J_C–P12.2 Hz), 132.07 (CH, J_C–P2.5 Hz), 133.19 (CH,

J_C–P9.7 Hz), 136.46 (CH), 136.63 (C_quat), 140.18 (C_quat, J_C–P14.6

2

H–H-COSY) 3.86 (3H, s, OCH₃), 4.46 (1H, d, J_P–H24.4 Hz),

8.04 (2H, d, ³J 8.6 Hz); δ_C(67.8 MHz, CDCl₃, DEPT 90, DEPT

135) 50.81 (¹J_C᎐P110.8 Hz, CH), 55.33 (OCH₃), 112.79 (J_C–P4.9

Hz), 140.37 (C_quat), 141.53 (C_quat), 184.35 (C_quat, C᎐O, ²J_C–P3.6

᎐

1

Hz); MS (FAB, 3-nitrobenzyl alcohol) m/z 483 (MH^ϩ, 84%).

Hz, CH), 119.71 (CH), 126.56 (CH), 127.10 (C_quat, J_C–P91.3

HRMS found: 483.1877; calcd. for C₃₄H₂₈OP: 483.1878 (MH^ϩ).

Hz), 127.40 (CH), 128.89 (CH, J_C–P12.1 Hz), 129.68 (CH),

132.05 (CH, J_C–P2.4 Hz), 133.19 (CH, J_C–P9.8 Hz), 140.16

(C_quat, J_C–P14.6 Hz), 141.88 (C_quat), 142.57 (C_quat), 159.91

(C_quat), 184.35 (²J_C–P3.6 Hz, C_quat); MS (FAB, 3-nitrobenzyl

alcohol) m/z 487 (MH^ϩ, 100%). HRMS found: 487.1832; calcd.

for C₃₃H₂₈O₂P: 487.1827 (MH^ϩ).

p-(2-Thienyl)benzoylmethylidenetriphenylphosphorane (4j)

A mixture of 3a (448 mg, 0.97 mmol), 2-thienylboronic acid

(250 mg, 1.95 mmol), Pd(PPh₃)₄(27 mg, 2.3 × 10^Ϫ2mmol) in

DME (5 mL) and 2 M aq. Na₂CO₃(3.7 mL) was reacted as

above (procedure A). After concentration of the organic phase

in vacuo, the residue was subjected to column chromatography

on silica gel (eluant ether) to give 3a (starting material; 32%),

R_f0.31, and 4j (264 mg, 58%), R_f0.16, mp 199–201 ЊC (ether)

(Found: C, 77.66; H, 5.08. C₃₀H₂₃OPS requires C, 77.90; H,

5.01%); ν_max(KBr)/cm^Ϫ13052, 1604, 1572, 1510, 1480, 1435,

1410, 1390, 1102, 880, 716, 691; δ_HNMR (270 MHz, CDCl₃)

4-(p-Fluorophenyl)benzoylmethylidenetriphenylphosphorane (4d)

A mixture of 3a (153 mg, 0.33 mmol), p-ﬂuorophenylboronic

acid (93 mg, 0.65 mmol) and Pd(PPh₃)₄(12.7 mg, 1.1 ×

10^Ϫ2mmol) in DME (3 mL) and 2 M aq. Na₂CO₃(1.3 mL) was

held at 75 ЊC for 5 h. Work-up according to general procedure

A and column chromatography on silica gel (eluant: ether) gave

4d (106 mg, 68%) as a colorless solid, mp; R_f0.21 (Found:

C, 80.82; H, 5.17. C₃₂H₂₄OFP requires C, 81.00; H, 5.10%); ν_max

(KBr)/cm^Ϫ13032, 2924, 1599, 1510, 1401, 1385, 1103, 880, 827,

691, 522, 505; δ_H(270 MHz, CDCl₃) 4.47 (1H, d, ³J_P–H23.1 Hz),

7.11 (3H, t, ³J 8.5 Hz), 7.44–7.60 (6H, m), 7.73–7.83 (12H, m),

8.04 (2H, d, ³J 7.9 Hz); δ_C(67.8 MHz, CDCl₃, DEPT 90, DEPT

2

4.44 (1H, d, J_H–P24.1 Hz), 7.07 (1H, m, thienyl-H), 7.26 (1H,

m, thienyl-H), 7.34 (1H, m, thienyl-H), 7.43–7.76 (17H, m),

7.97 (2H, d, ³J 7.9 Hz); δ_C(67.8 MHz, CDCl₃, DEPT 90, DEPT

1

135) 50.80 (CH, J_C᎐P112 Hz), 123.23 (CH), 124.90 (CH),

125.21 (CH), 127.54 (CH), 127.18 (C_quat, J_C–P90.3 Hz), 128.01

(CH), 128.89 (CH, J_C–P12.2 Hz), 132.07, (CH, J_C–P2.5 Hz),

133.16 (CH, J_C–P11.0 Hz), 135.16 (C_quat), 140.25 (C_quat, J_C–P

135) 50.80 (ϩ, CH, ¹J_C᎐P112.3 Hz), 115.55 (ϩ, CH, J 20.7 Hz),

᎐

14.6 Hz), 144.38 (C_quat), 184.04 (C᎐O, ²J_C–P2.5 Hz); MS (70 eV)

126.34 (ϩ, CH), 127.49 (ϩ, CH), 128.28 (C_quat, J_C–P70.7 Hz),

128.68 (ϩ, CH), 132.07 (ϩ, CH, J_C–P2.4 Hz), 133.09 (ϩ, CH,

12.1 Hz), 133.18 (ϩ, CH, J_C–P10.9 Hz), 137.18 (C_quat), 140.14

(C_quat, J_C–P, 14.6 Hz), 141.02 (C_quat), 162.49 (C_quat, J_C–F(Ϫ)

᎐

m/z 462 (M^ϩ, 100%), 303 ([M^ϩϪ Thienyl-Ph], 73); HRMS

found: 462.1209; calcd. for C₃₀H₂₃OPS: 462.1207.

245 Hz), 184.25 (C_quat, C᎐O, ²J_C–P2.4 Hz); MS (70 eV) m/z 474

᎐

p-(p-Triﬂuoromethylphenyl)benzoylmethylidenetriphenyl-

phosphorane (4k)

(M^ϩ, 100%), 303 (Ph₃PCHCO^ϩ, 66), 277 (85), 262 (41). HRMS

found: 474.1552; calcd. for C₃₂H₂₄OFP: 474.1549.

A mixture of 3a (263 mg, 0.57 mmol), p-triﬂuoromethylphenyl-

boronic acid (185 mg, 0.97 mmol), and Pd(PPh₃)₄(20 mg, 1.7 ×

10^Ϫ2mmol) in DME (3.5 mL) and 2 M aq. Na₂CO₃(2.3 mL)

were held at 75 ЊC for 9 h. Work-up according to procedure A

and column chromatography on silica gel (ether ether–ethyl

acetate 9 : 1) gave 4k (180 mg, 60%) as a pale yellow solid; mp

248–250 ЊC (ether) (Found: C, 75.27; H, 4.81.C₃₃H₂₄OF₃P

requires C, 75.57; H, 4.61%); ν_max(KBr)/cm^Ϫ13056, 2924, 1613,

1565, 1511, 1437, 1399, 1385, 1327, 1165, 1107, 1069, 885, 832,

750, 712; δ_H(270 MHz, CDCl₃) 4.50 (1H, br s), 7.44–7.78 (21H,

4-(2,4-Diﬂuorophenyl)benzoylmethylidenetriphenylphosphorane

(4e)

A mixture of 3a (153 mg, 0.33 mmol), 2,4-diﬂuorophenyl-

boronic acid (104 mg, 0.66 mmol) and Pd(PPh₃)₄(10 mg, 9.0 ×

10^Ϫ3mmol) in DME (3 mL) and 2 M aq. Na₂CO₃(1.3 mL) was

held at 75 ЊC for 5 h. Work-up according to general procedure

A and column chromatography on silica gel (ether) gave 4e

(108 mg, 66%) as colorless rhombic crystals, mp 190–192 ЊC

(ether) (Found: C, 77.97; H, 4.75. C₃₂H₂₃OF₂P requires C,

78.04; H, 4.71%); ν_max(KBr)/cm^Ϫ13052, 2924, 1598, 1573, 1514,

1492, 1481, 1436, 1401, 1385, 1103, 885, 846, 714; δ_H(270 MHz,

3

m), 8.07 (2H, d, J 8.2 Hz); δ_C(67.8 MHz, CDCl₃, DEPT 90,

DEPT 135) 51.21 (CH, ¹J_C–P112.3 Hz), 125.67 (CH, J 3.7 Hz),

126.70 (CH), 126.99 (C_quat, ¹J_C–P90.2 Hz), 127.42 (CH), 127.65

2

1

CDCl₃) 4.48 (1H, d, J_P–H24.1 Hz), 6.92 (2H, m), 7.37–7.77

(CH), 128.95 (CH, J_C–P12.1 Hz), 129.57 (C_quat, CF₃, J_C–F

3

(18H, m), 8.04 (2H, d, J 7.9 Hz); δ_C(67.8 MHz) 51.23 (¹J_C᎐P

(Ϫ)270 Hz), 129.80 (C_quat), 132.13 (CH, J_C–P2.4 Hz), 133.18

(CH, J_C–P11.0 Hz), 140.46 (C_quat), 141.07 (C_quat, J_C–P14.7 Hz),

᎐

112.3 Hz), 104.33 (²J_C–F25.6, ²J_C–F25.6 Hz), 111.48 (²J_C–F20.7,

⁴J_C–F3.7 Hz), 127.02 (J_C–P90.2 Hz), 127.13, 128.35 (J_C–P2.4

Hz), 128.91 (J_C–P12.1 Hz), 132.09, 133.28 (J_C–P9.0 Hz), 133.45,

2

144.56 (C_quat), 184.03 (C_quat, C᎐O, J 3.7 Hz); MS (FAB, 3-

᎐

C–P

nitrobenzyl alcohol) 525 (MH^ϩ, 100%), 307 (19). HRMS found:

525.1597; calcd. for C₃₃H₂₅OF₃P: 525.1595 (MH^ϩ).

3

135.88, 140.61 (J 14.6 Hz), 159.21 (¹J_C–F169.7, J_C–F12.2 Hz),

J. Chem. Soc., Perkin Trans. 1, 2002, 2090–2110

2099

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p-(2-Naphthyl)benzoylmethylidenetriphenylphosphorane (4l)

4-(Dibenzo[b,d]thiophen-3-yl)benzoylmethylidenetriphenyl-

phosphorane (4o)

A mixture of 3a (263 mg, 0.57 mmol), 2-naphthylboronic acid

(167 mg, 0.97 mmol), and Pd(PPh₃)₄(20 mg, 1.7 × 10^Ϫ2mmol)

in DME (3.5 mL) and 2 M aq. Na₂CO₃(2.3 mL) were held at

75 ЊC for 6 h. Work-up according to procedure A and column

chromatography on silca gel (ether ether–ethyl acetate 9 : 1)

gave 4l (261 mg, 90%) as pale yellow needles; mp 205-206 ЊC

(ether); ν_max(KBr)/cm^Ϫ13052, 1569, 1517, 1381, 1105, 883,

747, 717, 693; δ_H(270 MHz, CDCl₃) 4.52 (1H, br s), 7.44–7.59

(11H, m), 7.70–7.79 (9H, m), 7.83–7.91 (3H, m), 8.11 (3H, m);

δ_C(67.8 MHz, CDCl₃, DEPT 90, DEPT 135) 50.87 (CH,

¹J_C᎐P112.07 Hz), 125.60 (CH), 125.78 (CH), 125.89 (CH),

126.23 (CH), 126.77 (CH), 127.14 (C_quat, ¹J_C–P91.3 Hz), 127.54

(CH), 127.63 (CH), 128.25 (CH), 128.33 (CH), 128.91 (CH,

J_C–P12.1 Hz), 132.07 (CH, J_C–P2.4 Hz), 132.68 (C_quat), 133.20

A mixture of 3a (153 mg, 0.33 mmol), dibenzothienylboronic

acid (150 mg, 0.66 mmol) and Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3

mmol) in DME (3 mL) and 2 M aq. Na₂CO₃(1.3 mL) were held

at 75 ЊC for 9 h. Work-up according to general procedure A and

column chromatography on silica gel (ether) gave 4o (158 mg,

85%) as a colorless solid; R_f0.14 (ether); mp 267–269 ЊC (ether)

(Found: C, 81.05; H, 4.84. C₃₈H₂₈OPS requires C, 80.96; H,

5.00%); ν_max(KBr)/cm^Ϫ13054, 1571, 1518, 1480, 1438, 1411,

1386, 1105, 883, 746, 693; δ_H(270 MHz, CDCl₃) 4.52 (1H, d,

²J_P–H24.1 Hz), 7.47–7.59 (9H, m), 7.27–7.35 (13H, m), 7.73–

8.05 (4H, m); δ_C(67.8 MHz, CDCl₃, DEPT 90,DEPT 135)

51.10 (CH, ¹J_C᎐P112.07 Hz), 120.43 (CH), 121.69 (CH), 122.62

᎐

(CH), 124.31 (CH), 125.05 (CH), 126.73 (CH), 126.92 (CH),

127.46 (CH), 127.73 (CH), 127.05 (C_quat, ¹J_C–P91.4 Hz), 128.92

(CH, J_C–P13.4 Hz), 132.11 (CH, J_C–P2.4 Hz), 133.20 (CH, J_C–P

18.3 Hz), 135.77 (C_quat), 136.21 (C_quat), 136.98 (C_quat), 138.63

(C_quat), 139.68 (C_quat), 140.92 (C_quat, J_C–P15.9 Hz), 141.51

(CH, J_C–P9.8Hz), 133.69(C_quat), 138.36(C_quat), 140.23(C_quat, J_C–P

2

14.6 Hz), 141.92 (C_quat), 184.38 (C_quat, C᎐O, J 2.4 Hz); MS

᎐

C–P

(FAB, 3-nitrobenzyl alcohol) m/z 507 (100%, MH^ϩ); 303 (28).

HRMS found: 507.1882; calcd. for C₃₆H₂₈OP: 507.1878 (MH^ϩ,

FAB).

(C_quat), 184.30 (C_quat, J_C–P3.7 Hz, C᎐O); MS (70 eV) m/z 563

᎐

(MH^ϩ, 100%), 303 (36). HRMS found: 563.1597 (MH^ϩ); calcd.

for C₃₈H₂₈OPS: 563.1599.

4-[p-(1,3-Dioxan-2-yl)phenyl]benzoylmethylidenetriphenylphos-

phorane (4m)

4-[3,5-Bis(trimethylsilylethynyl)phenyl]benzoylcarbonylmethyl-

idenetriphenylphosphorane (4p)

A mixture of 3a (153 mg, 0.33 mmol), p-(1,3-dioxan-2-yl)-

phenylboronic acid (164 mg, 0.66 mmol), CsF (400 mg,

2.64 mmol) and Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3mmol) in DME

(8 mL) were held at 75 ЊC for 3 h. The cooled solution was

diluted with water (10 mL) and extracted with chloroform (3 ×

10 mL). The organic phase was dried over anhydrous MgSO₄

and concentrated in vacuo. Column chromatography on silica

gel [eluant: ether ether–ethyl acetate (1.5 : 10)] to give 4m

(64 mg, 36%) as a colorless crystalline solid, mp 120 ЊC; ν_max

(KBr)/cm^Ϫ13050, 2964, 2846, 1582, 1565, 1511, 1482, 1436,

1386, 1148, 1102, 1005, 996, 879, 853, 823, 748, 718; δ_H(270

MHz, CDCl₃) 2.24 (2H, m), 4.02 (2H, m), 4.28 (2H, dd, ²J 15.9,

³J 4.9 Hz), 4.45 (1H, br s), 5.54 (1H, s), 7.45–7.77 (21H, m), 8.03

A mixture of 3a (150 mg, 0.33 mmol), 3,5-bis(trimethylsilyl-

ethynyl)phenylboronic acid (314 mg, 1.0 mmol) and Pd(PPh₃)₄

(10 mg, 9.0 × 10^Ϫ3mmol) in DME (3.0 mL) and 2 M aq. Na₂-

CO₃(1.2 mL) was held at 75 ЊC for 7 h. Work-up according to

general procedure A and column chromatography on silica gel

(ether) gave 4p (34 mg, 16%) as a pale yellow oil; R_f0.23 (ether);

ν_max(neat)/cm^Ϫ13058, 2954, 2150, 1656, 1564, 1510, 1438, 1406,

1387, 1249, 1106, 881, 842, 690; δ_H(270 MHz, CDCl₃) 0.26

(9H, s, 3 CH₃), 0.28 (9H, s, 3 CH₃), 4.49 (1H, v br s), 7.49–7.76

(20H, m), 7.94 (2H, d, ³J 7.9 Hz); δ_C(67.8 MHz, CDCl₃, DEPT

90, DEPT 135) Ϫ1.26 (ϩ, 6 × CH₃), 51.49 (ϩ, CH, ¹J_C᎐P113.5

Hz), 94.60 (C_quat), 104.43 (C_quat), 122.80 (C_quat), 122.90^᎐(C_quat),

3

1

(2H, d, J 7.9 Hz); δ_CNMR (CDCl₃, DEPT 90, DEPT 135)

123.85 (C_quat), 126.92 (C_quat, J_C–P91.4 Hz), 127.01 (ϩ, CH),

1

26.31 (Ϫ), 51.19 (CH, J_C᎐P110.8 Hz), 67.82 (Ϫ), 101.96 (ϩ,

128.98 (ϩ, CH, J_C–P12.2 Hz), 131.19 (ϩ, CH), 132.20 (ϩ, CH),

133.22 (ϩ, CH, J_C–P9.8 Hz), 135.27 (ϩ, CH), 136.26 (ϩ, CH),

CH), 126.93 (CH, J 9.7 Hz), 127.47 (CH), 127.76 (C_quat, J 90.0

Hz), 127.89 (CH), 128.93 (CH, J 12.2 Hz), 129.33 (CH, J 12.2

Hz), 132.40 (C_quat, J 6.1 Hz), 132.58 (CH, J 9.7 Hz), 133.67

(CH, J 9.8 Hz), 138.33 (C_quat), 140.81 (C_quat, J 14.6 Hz), 142.11

141.13 (C_quat), 183.99 (C_quat, C᎐O); MS (FAB, 3-nitrobenzyl

᎐

alcohol) m/z 649 (MH^ϩ, 100%), 303 (22), 275 (23). HRMS

found: 649.2515; calcd. for C₄₂H₄₂OSi₂P: 649.2512 (MH^ϩ).

(C_quat, J 18.3 Hz), 184.94 (C_quat, C᎐O, ²J_C–P2.4 Hz); MS (70 eV)

᎐

p-(o-Tolyl)benzoylmethylidenetriphenylphosphorane (4q)

m/z 277 (100%); MS (FAB, 3-nitrobenzyl alcohol) m/z (%) 543

(MH^ϩ, 46). HRMS found: 543.2092; calcd. for C₃₆H₃₂O₃P:

543.2089 (MH^ϩ).

A mixture of 3a (263 mg, 0.57 mmol), o-tolylboronic acid

(132 mg, 0.97 mmol), Pd(PPh₃)₄(20 mg, 1.7 × 10^Ϫ2mmol) in

2 M Na₂CO₃(2.3 mL) and DME (3 mL) was held at reﬂux for

5 h. Thereafter the cooled reaction mixture was worked up

according to procedure A. Column chromatography on silica

gel (ether ether–ethyl acetate 9 : 1) gave 4q (147 mg, 55%) as

colorless needles; mp 261–262 ЊC (ether) (Found: C, 83.96; H,

5.89. C₃₃H₂₇OP requires C, 84.23; H, 5.79%); ν_max(KBr)/cm^Ϫ1

3056, 1578, 1513, 1481, 1438, 1408, 1386, 1105, 885, 750, 692;

δ_H(270 MHz, CDCl₃) 2.27 (3H, s, CH₃), 4.47 (1H, d, ²J_P–H24.4

4-(1-Benzothiophen-2-yl)benzoylmethylidenetriphenylphos-

phorane (4n)

A mixture of 3a (153 mg, 0.33 mmol), 1-benzothiophen-2-yl-

boronic acid (150 mg, 0.84 mmol) and Pd(PPh₃)₄(10 mg, 9.0 ×

10^Ϫ3mmol) in DME (3 mL) and 2 M aq. Na₂CO₃(1.3 mL) was

held at 75 ЊC for 10 h. Work-up according to general procedure

A and column chromatography on silica gel (ether) gave 4n

(165 mg, 98%) as a colorless solid, mp 254–256 ЊC (ether)

(Found: C, 79.21; H, 4.94. C₃₄H₂₆OPS requires C, 79.51; H,

5.10%); ν_max(KBr)/cm^Ϫ13052, 1602, 1572, 1512, 1436, 1407,

1386, 1105, 881, 761, 745, 717, 691; δ_H(270 MHz, CDCl₃) 4.47

3

Hz), 7.24 (4H, m), 7.31 (2H, d, J 8.1 Hz), 7.44–7.59 (9H, m),

7.70–7.78 (6H, m), 8.01 (2H, d, ³J 8.3 Hz); δ_C(67.8 MHz,

CDCl₃, DEPT 90, DEPT 135) 20.49 (ϩ, CH₃), 50.74 (ϩ, CH,

¹J_C᎐P112.1 Hz), 125.69 (CH), 126.72 (CH), 127.13 (C_quat, J_C–P

1

90.1 Hz), 127.20 (CH), 128.68 (CH), 128.89 (CH, J_C–P12.1 Hz),

129.74 (CH), 130.28 (CH), 132.06 (CH, J_C–P2.4 Hz), 133.19

(CH, J_C–P9.8 Hz), 135.42 (C_quat), 139.79 (C_quat, J_C–P13.4 Hz),

2

3

(1H, d, J_P–H24.1 Hz), 7.27–7.83 (22H, m), 8.03 (2H, d, J 8.3

Hz); δ_C(67.8 MHz, CDCl₃, DEPT 90, DEPT 135) 51.01 (CH,

¹J_C᎐P112.5 Hz), 119.64 (CH), 122.24 (CH), 123.57 (CH), 124.31

141.88 (C_quat), 143.02 (C_quat), 184.66 (C_quat, C᎐O, ²J_C–P3.7 Hz);

1

᎐

(CH), 124.47 (CH), 125.84 (CH), 126.92 (C_quat, J_C–P92.6 Hz),

MS (FAB, 3-nitrobenzyl alcohol) m/z 471 (MH^ϩ, 100%);

127.60 (CH), 128.57 (C_quat), 128.95 (CH, J_C–P12.1 Hz), 133.12

(CH, br s), 133.19 (CH, J_C–P9.8 Hz), 135.00 (C_quat), 139.58

HRMS found: 471.1884; calcd. for C₃₃H₂₈OP: 471.1878.

(C_quat), 140.70 (C_quat), 144.13 (C_quat, br s), 183.72 (C_quat, C᎐O);

᎐

1,4-Bis[(triphenylphosphoranylidene)acetyl]benzene (4r)

MS (FAB, 3-nitrobenzyl alcohol) m/z 513 (MH^ϩ, 52%), 307

(42), 154 (100). HRMS found: 513.1446 (MH^ϩ); calcd. for

C₃₄H₂₆OPS: 513.1442.

A mixture of 3a (459 mg, 1.0 mmol), 1,4-phenylenediboronic

acid (83 mg, 0.5 mmol) and Pd(PPh₃)₄(30 mg, 2.5 × 10^Ϫ2mmol)

2100

J. Chem. Soc., Perkin Trans. 1, 2002, 2090–2110

View Article Online

in DME (4 mL) and 2 M aq. Na₂CO₃(2 mL) was held at 75 ЊC

for 11 h. Thereafter water (10 mL) was added to the cooled

reaction mixture and the suspension was extracted with chloro-

form (3 × 10 mL). The organic phase was dried over anhydrous

MgSO₄and concentrated in vacuo until about 5 mL of solution

remained. To this was added ether (20 mL). The precipitate

formed was ﬁltered, washed with ether (10 mL) and dried

in vacuo to give 4r (270 mg, 65%) as a greyish powder; ν_max

(KBr)/cm^Ϫ13052, 1576, 1515, 1388, 885, 755, 718, 692; δ_H(270

MHz, CDCl₃) 4.49 (2H, br s), 7.44–7.77 (34H, m), 7.70 (4H, s),

8.06 (4H, d, ³J 8.2 Hz); δ_C(67.8 MHz, CDCl₃, DEPT 90, DEPT

was dried and concentrated in vacuo. The residue was recrystal-

lized in ether to give 5c (91 mg, 57%) as yellow crystals, mp 210–

216 ЊC (Found C, 73.42; H, 5.12. C₃₀H₂₂OSFPؒ0.5H₂O requires

C, 73.60; H, 4.73%); ν_max(KBr)/cm^Ϫ13045, 2900, 1500, 1430,

1370, 1217, 1155, 1095, 863, 840, 798, 685; δ_H(270 MHz,

CDCl₃) 4.31 (1H, ill-resolved d), 7.04 (2H, dd, ³J 8.9, ³J 8.6 Hz),

3

7.15 (1H, d, J 2.5 Hz), 7.26–7.75 (18H, m); δ_C(67.9 MHz,

CDCl₃) 50.45 (¹J_C᎐P113.5 Hz), 123.27, 126.16, 128.96 (J_C–P12.1

᎐

Hz), 132.20 (J 2.4 Hz), 133.21 (J_C–P9.8 Hz), 144.61, 147.74

(J 17.1 Hz), 162.37 (¹J_C–F246.1 Hz), 178.02 (²J_C–P4.9 Hz);

MS (FAB, 3-nitrobenzyl alcohol) m/z 481 (MH^ϩ, 100%), 303

(Ph₃PCHCO^ϩ, 20). HRMS found: 481.1190; calcd. for C₃₀H₂₃-

OFPS: 481.1191 (MH^ϩ).

1

135) 51.47 (CH, J_C᎐P112.07 Hz), 126.85 (CH), 127.91 (CH),

127.52 (C_quat, ¹J_C–P91.4 Hz), 129.34 (CH, J_C–P12.2 Hz), 132.52

(CH, J_C–P13.4 Hz), 133.64 (CH, J_C–P9.8 Hz), 140.39 (C_quat),

140.59 (C_quat, J_C–P14.6 Hz), 142.01 (C_quat), 184.84 (C_quat, C᎐O,

᎐

5-(2,4-Diﬂuorophenyl)-2-thienylcarbonylmethylidenetriphenyl-

phosphorane (5e)

²J_C–P3.7 Hz); MS (FAB, 3-nitrobenzyl alcohol) m/z 835 (MH^ϩ,

5%). HRMS found: 835.2893; calcd. for C₅₈H₄₅O₂P₂: 835.2895

(MH^ϩ).

A mixture of 3b (77 mg, 0.17 mmol), 2,4-diﬂuorophenylboronic

acid (93 mg, 0.66 mmol) and Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3

mmol) in DME (3 mL) and 2 M aq. Na₂CO₃(1.3 mL) was held

at 75 ЊC for 5 h. Work-up according to general procedure A and

column chromatography on silica gel (ether) gave 5e (64 mg,

78%) as a pale yellow solid, mp 202–203 ЊC (ether), R_f0.38

(ether); ν_max(KBr)/cm^Ϫ13050, 1505, 1440, 1380, 1105, 880;

5-Phenyl-2-thienylcarbonylmethylidenetriphenylphosphorane

(5a)

A mixture of 3b (153 mg, 0.33 mmol), phenylboronic acid

(80 mg, 0.66 mmol) and Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3mmol)

in DME (3 mL) and 2 M aq. Na₂CO₃(1.3 mL) was held at

75 ЊC for 11 h. Work-up according to general procedure A and

column chromatography on silica gel (ether) gave 5a (95 mg,

62%) as a yellow solid; mp 194–196 ЊC (ether) (Found: C, 77.60;

H, 4.99. C₃₀H₂₃OPS requires C, 77.91; H, 5.01%); ν_max(KBr)/

cm^Ϫ13052, 1539, 1519, 1481, 1453, 1438, 1386, 1107, 870, 748,

732, 714, 691; δ_H(270 MHz, CDCl₃) 4.31 (1H, d, ²J_H–P22.8 Hz),

7.25 (2H, m), 7.33 (2H, m), 7.47–7.75 (18H, m); δ_C(67.8 MHz,

2

δ_H(270 MHz, CDCl₃) 4.33 (1H, d, J 22.1 Hz), 6.88 (2H, m),

3

7.32 (1H, d, J 3.6 Hz), 7.46–7.75 (17H, m); δ_C(67.8 MHz,

1

CDCl₃, DEPT 90, DEPT 135) 50.61 (CH, J_C᎐P113.4 Hz),

104.60 (CH, J_C–F25.6, J_C–F25.6 Hz), 111.73 (CH, J_C–F20.7, J_C–F

3.6 Hz), 126.42 (C_quat) 126.50 (CH), 126.63 (CH), 126.80 (C_quat

,

¹J_C–P91.6 Hz), 128.96 (CH, J_C–P12.2 Hz), 129.68 (CH, J 9.7,

J 4.8 Hz), 132.22 (CH, J_C–P2.5 Hz), 133.21 (CH, J_C–P9.8 Hz),

137.57 (C_quat), 148.36 (C_quat, J 20.7 Hz), 158.75 (C_quat, J_C–F

1

3

CDCl₃, DEPT 90, DEPT 135) 50.14 (ϩ, CH, J_C᎐P113.7 Hz),

183.8, J_C–F12.1 Hz), 162.41 (C_quat, J_C–F182.3, J_C–F12.1 Hz),

122.32 (ϩ, CH), 125.96 (ϩ, CH), 127.01 (ϩ, CH), 127.23 (C_quat

,

177.89 (C_quat,

²J_C–P4.9 Hz, C᎐O); MS (FAB, 3-nitrobenzyl

᎐

¹J_C᎐P91.6 Hz), 127.49 (ϩ, CH), 128.96 (ϩ, CH, J_C–P13.4 Hz),

132.16 (ϩ, CH, J_C–P2.4 Hz), 133.31 (ϩ, CH, J_C–P9.8 Hz),

alcohol) m/z 499 (MH^ϩ, 100%), 303 (Ph₃PCHCO^ϩ, 24). HRMS

found: 499.1093; calcd. for C₃₀H₂₂OF₂PS: 499.1097.

134.98 (C_quat), 145.84 (C_quat), 147.88 (C_quat, J_C–P18.3 Hz), 178.32

2

(C_quat, C᎐O, J

3.7 Hz); MS (FAB, 3-nitrobenzyl alcohol)

᎐

C–P

5-(p-Vinylphenyl)-2-thienylcarbonylmethylidenetriphenylphos-

phorane (5f)

m/z 463 (MH^ϩ, 41%). HRMS found: 463.1278; calcd. for

C₃₀H₂₄OPS: 463.1286.

A mixture of 3b (69 mg, 0.15 mmol), p-vinylphenylboronic acid

(44 mg, 0.29 mmol) and Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3mmol) in

DME (1.5 mL) and 2 M aq. Na₂CO₃(0.6 mL) was held at 75 ЊC

for 5 h. Work-up according to general procedure A and column

chromatography on silica gel [ether ethyl acetate–ether (1 : 4)]

gave 5f (69 mg, 95%) as a yellow solid, mp 221–223 ЊC (ether);

ν_max(KBr)/cm^Ϫ13050, 1509, 1450, 1436, 1387, 1105, 874, 692,

505; δ_H(270 MHz, CDCl₃) 4.32 (1H, br s), 5.24 (1H, d, ³J 10.9

Hz), 5.75 (1H, d, ³J 17.5 Hz), 6.71 (1H, dd, ³J 17.5, ³J 10.9 Hz),

7.25 (1H, m), 7.38–7.60 (16H, m), 7.69 (2H, d, ³J 7.9 Hz), 7.74

(2H, d, ³J 7.6 Hz); δ_C(67.8 MHz, CDCl₃, DEPT 90, DEPT 135)

5-(p-Methoxyphenyl)-2-thienylcarbonylmethylidenetriphenyl-

phosphorane (5b)

A mixture of 3b (154 mg, 0.33 mmol), p-methoxyphenylboronic

acid (150 mg, 1.0 mmol) and Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3

mmol) in DME (3 mL) and 2 M aq. Na₂CO₃(1.3 mL) was held

at 75 ЊC for 5 h. Work-up according to general procedure A and

column chromatography on silica gel [eluant: ether ethyl

acetate–ether (1 : 10)] gave 5b (117 mg, 72%) as a pale yellow

solid, mp 205–207 ЊC (ether) (Found: C, 75.07; H, 5.26. C₃₁H₂₅-

O₂PSؒ0.25H₂O requires C, 74.91; H, 5.17%); ν_max(KBr)/cm^Ϫ1

3050, 2836, 1516, 1452, 1438, 1387, 1251, 1104, 730, 693, 505;

δ_H(270 MHz, CDCl₃) 3.82 (3H, s, OCH₃), 4.23 (1H, ill-resolved

1

50.34 (CH, J_C᎐P113.3 Hz), 113.75 (Ϫ, CH₂), 122.27 (CH),

125.89 (CH), 126.68 (CH), 127.01 (C_quat, ¹J_C–P91.4 Hz), 127.04

(CH), 128.93 (CH, J_C–P12.2 Hz), 132.15 (CH, J_C–P2.4 Hz),

133.23 (CH, J_C–P10.9 Hz), 134.27 (C_quat), 136.41 (CH), 136.85

3

d), 6.89 (2H, d, J 8.9 Hz), 7.12 (1H, d, J 3.6 Hz), 7.26–7.59

(12H, m), 7.67–7.76 (6H, m); δ_C(67.8 MHz, CDCl₃) 50.05 (¹J_C᎐P

(C_quat), 145.43 (C_quat), 147.49 (C_quat, J_C–P17.7 Hz), 178.13 (C_quat,

᎐

112.1 Hz), 55.33 (OCH₃), 114.23, 122.26, 126.27, 127.04,

127.64, 128.89 (J_C–P12.2 Hz), 132.11, 133.18 (J_C–P11.0 Hz),

145.76, 146.57 (J_C–P18.2 Hz), 159.26, 178.26 (²J_C–P3.7 Hz,

C᎐O); MS (70 eV) m/z 492 (M^ϩ, 100%), 303 (Ph PCHCO^ϩ, 56),

²J_C–P3.7 Hz, C᎐O); MS (FAB, 3-nitrobenzyl alcohol) m/z 489

᎐

(MH^ϩ, 100%), 303 (40). HRMS found: 489.1449; calcd. for

C₃₂H₂₆OPS: 489.1442 (MH^ϩ).

᎐

3

291 (49), 262 (51), 232 (50), 183 (63). HRMS found: 493.1393;

5-(Dibenzo[b,d]thiophen-3-yl)-2-thienylcarbonylmethylidenetri-

phenylphosphorane (5h)

calcd. for C₃₁H₂₆O₂PS: 493.1391 (MH^ϩ).

A mixture of 3b (153 mg, 0.33 mmol), dibenzothienylboronic

acid (150 mg, 0.66 mmol) and Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3

mmol) in DME (3 mL) and 2 M aq. Na₂CO₃(1.3 mL) was held

at 75 ЊC for 12 h. Work-up according to general procedure A

and column chromatography on silica gel (ether) gave 5h

(124 mg, 66%) as a yellow solid (Found: C, 75.95; H, 4.57.

C₃₆H₂₅OPS₂requires C, 76.03; H, 4.43%); ν_max(KBr)/cm^Ϫ13056,

1539, 1516, 1480, 1461, 1436, 1382, 1106, 885, 745, 732, 714;

5-(p-Fluorophenyl)-2-thienylcarbonylmethylidenetriphenylphos-

phorane (5c)

A mixture of 3b (154 mg, 0.33 mmol), p-ﬂuorophenylboronic

acid (93 mg, 0.66 mmol) and Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3

mmol) in DME (3 mL) and 2 M aq. Na₂CO₃(1.3 mL) was held

at 75 ЊC for 5 h. The reaction mixture was poured into water

and extracted with chloroform (3 × 30 mL). The organic phase

J. Chem. Soc., Perkin Trans. 1, 2002, 2090–2110

2101

View Article Online

2

δ_H(270 MHz, CDCl₃) 4.36 (1H, d, J_P–H22.8 Hz), 7.42–7.79

747, 734, 718; δ_H(270 MHz, CDCl₃) 1.75 (3H, s, CH₃), 4.31

(1H, d, ²J_P–H23.1 Hz), 6.98 (1H, d, ³J 4.0 Hz), 7.19–7.76 (20H,

m); δ_C(67.8 MHz, CDCl₃, DEPT 90, DEPT 135) 21.08 (ϩ,

3

(22H, m), 7.87 (1H, m), 8.09 (1H, d, J 9.0 Hz), 8.16 (1H, m);

δ_C(67.8 MHz, CDCl₃, DEPT 90, DEPT 135) 50.65 (ϩ, CH,

¹J_C᎐P113.3Hz), 120.59(ϩ, CH), 121.65(ϩ, CH), 122.61(ϩ, CH),

124.44 (ϩ, CH), 124.92 (ϩ, CH), 125.88 (ϩ, CH), 126.41 (ϩ,

1

CH₃), 50.23 (ϩ, CH, J_C᎐P113.5 Hz), 125.84 (ϩ, CH), 126.13

1

(ϩ, CH), 126.74 (ϩ, CH), 126.87 (C_quat, J_C–P91.5 Hz), 127.69

CH), 126.70 (ϩ, CH), 126.82 (C_quat

,

¹J_C–P91.3 Hz), 126.85

(ϩ, CH), 128.66 (C_quat), 128.91 (ϩ, CH, J_C–P12.2 Hz), 130.28

(ϩ, CH), 130.69 (ϩ, CH), 132.13 (ϩ, CH, J_C–P2.4 Hz), 133.17

(ϩ, CH, J_C–P9.8 Hz), 136.05 (C_quat), 144.83 (C_quat), 147.90

(ϩ, CH), 128.93 (ϩ, CH, J_C–P12.2 Hz), 130.22 (C_quat), 132.17

(ϩ, CH, J_C–P3.7 Hz), 133.20 (ϩ, CH, J_C–P10.9 Hz), 135.54

(C_quat), 136.57 (C_quat), 137.52 (C_quat), 139.57 (C_quat), 143.79

(C_quat), 148.35 (C_quat, J_C–P18.2 Hz), 177.96 (C_quat, ²J_C–P3.6 Hz);

MS (FAB, 3-nitrobenzyl alcohol) m/z 569 (MH^ϩ, 100%), 303

(50). HMRS found: 569.1171; calcd. for C₃₆H₂₆OPS₂: 569.1163

(MH^ϩ).

(C_quat, J 17.1 Hz), 178.29 (C_quat, C᎐O); MS (FAB, 3-nitrobenzyl

᎐

alcohol) m/z 477 (MH^ϩ, 28%). HRMS found: 477.1440; calcd.

for C₃₁H₂₆OPS: 477.1442.

(2,2Ј-Bithiophen-5-yl)carbonylmethylidenetriphenylphosphorane

(5l)

5-(1-Benzothiophen-2-yl)-2-thienylcarbonylmethylidenetri-

phenylphosphorane (5i)

A mixture of 3b (153 mg, 0.33 mmol), 2-thienylboronic acid

(84 mg, 0.66 mmol) and Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3mmol) in

DME (3 mL) and 2 M aq. Na₂CO₃(1.3 mL) was held at 75 ЊC

for 5 h. Work-up according to general procedure A and column

chromatography on silica gel [ether ethyl acetate–ether (1 : 4)]

gave 5l (20 mg, 13%) as a yellow solid, mp 193–194 ЊC (ether),

R_f0.14 (ether) (Found: C, 71.65; H, 4.63. C₂₈H₂₁OS₂P requires

C, 71.77; H, 4.52%); ν_max(KBr)/cm^Ϫ13080, 1527, 1517, 1443,

1395, 1115, 875, 815, 740, 700; δ_H(270 MHz, CDCl₃) 4.28 (1H,

A mixture of 3b (153 mg, 0.33 mmol), 1-benzothiophen-2-

ylboronic acid (120 mg, 0.67 mmol) and Pd(PPh₃)₄(10 mg, 9.0

× 10^Ϫ3mmol) in DME (3 mL) and 2 M aq. Na₂CO₃(1.3 mL)

was held at 75 ЊC for 9 h. Work-up according to general pro-

cedure A and column chromatography on silica gel (ether) gave

5i (84 mg, 49%) as a yellow solid; R_f0.14 (ether); mp 222–225

ЊC (ether) (Found: C, 74.02; H, 4.55. C₃₂H₂₃OPS₂requires C,

74.07; H, 4.47%); ν_max(KBr)/cm^Ϫ13052, 1524, 1508, 1435, 1388,

1105, 871, 744, 731, 714, 692; δ_H(270 MHz, CDCl₃) 4.31 (1H,

d, J_H–P22.8 Hz), 7.20 (1H, d, J 3.6 Hz), 7.23–7.75 (21H, m);

δ_C(67.8 MHz, CDCl₃, DEPT 90, DEPT 135) 50.72 (ϩ, CH,

¹J_C᎐P113.3Hz), 119.69(ϩ, CH), 122.05(ϩ, CH), 123.40(ϩ, CH),

124.37 (ϩ, CH), 124.56 (ϩ, CH), 125.19 (ϩ, CH), 126.65 (ϩ,

CH), 126.71 (C_quat, ¹J_C–P91.3 Hz), 128.93 (ϩ, CH, J_C–P12.2 Hz),

132.22 (ϩ, CH), 133.15 (ϩ, CH, J_C–P9.7 Hz), 137.77 (C_quat),

2

3

d, J_H–P22.8 Hz), 7.00 (1H, m), 7.09 (1H, d, J 4.0 Hz), 7.18

(2H, m), 7.41–7.75 (16H, m); δ_C(67.8 MHz, CDCl₃) 51.35 (¹J_C᎐P

113.4 Hz), 124.69, 124.76, 127.60, 127.75 (¹J_C–P91.4 Hz^᎐),

128.70, 129.85 (J_C–P12.3 Hz), 133.08 (⁴J_C–P2.4 Hz), 134.11 (J_C–P

9.8 Hz), 138.92, 139.75, 148.09 (³J_C–P18.3 Hz), 178.79 (²J_C–P3.7

Hz, C᎐O); MS (70 eV) m/z 468 (M^ϩ, 100%), 303 (Ph PCHCO^ϩ,

2

3

᎐

3

66), 183 (74). HRMS found: 469.0850; calcd. for C₂₈H₂₂OPS₂:

469.0850 (MH^ϩ, FAB).

138.62 (C_quat), 139.19 (C_quat), 140.40 (C_quat), 148.53 (C_quat, J_C–P

2

18.3 Hz), 177.60 (C_quat, C᎐O, J_C–P3.7 Hz); MS (FAB,

᎐

5-(m-Nitrophenyl)-2-thienylcarbonylmethylidenetriphenyl-

phosphorane (5m)

3-nitrobenzyl alcohol) m/z 519 (MH^ϩ, 28%). HRMS found:

519.1004; calcd. for C₃₂H₂₄OPS₂: 519.1006 (MH^ϩ).

A mixture of 3b (154 mg, 0.33 mmol), m-nitrophenylboronic

acid (110 mg, 0.66 mmol) and Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3

mmol) in DME (3 mL) and 2 M aq. Na₂CO₃(1.3 mL) was held

at 75 ЊC for 5 h. Work-up according to general procedure A and

column chromatography on silica gel gave 5m (150 mg, 89%) as

a yellow solid, mp 203–207 ЊC (ether) (Found: C, 70.54; H, 4.47;

N, 2.82. C₃₀H₂₂O₃NPS requires C, 71.00; H, 4.37; N, 2.76%);

ν_max(KBr)/cm^Ϫ13050, 1512, 1375, 1340, 1095, 870; δ_H(270

MHz, CDCl₃) 4.35 (1H, d, J_P–H18.1 Hz), 7.36 (1H, d, J 2.0

Hz), 7.47–7.91 (18H, m), 8.10 (1H, dd, J 8.3, J 2.0 Hz), 8.46

(1H, s); δ_C(67.8 MHz, CDCl₃) 51.04 (J_C᎐P113.3 Hz), 120.25,

121.80, 124.91, 126.62 (¹J_C–P91.3 Hz), 127.01, 129.00 (J 12.1

Hz), 129.79, 131.39, 132.29 (J 2.4 Hz), 133.18 (J 10.9 Hz),

5-(2-Naphthyl)-2-thienylcarbonylmethylidenetriphenylphos-

phorane (5j)

A mixture of 3b (153 mg, 0.33 mmol), 2-naphthylboronic acid

(114 mg, 0.66 mmol) and Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3mmol) in

DME (3 mL) and 2 M aq. Na₂CO₃(1.3 mL) was held at 75 ЊC

for 12 h. Work-up according to general procedure A and

column chromatography on silica gel (ether) gave 5j (122 mg,

72%) as a yellow solid; mp 248–249 ЊC (ether); R_f0.12 (ether)

(Found: C, 79.46; H, 5.05. C₃₄H₂₅OPS requires C, 79.66; H,

4.90%); ν_max(KBr)/cm^Ϫ13050, 1542, 1511, 1476, 1438, 1381,

1147, 1105, 1080, 871, 853, 813, 732, 716, 692; δ_H(270 MHz,

2

3

2

3

CDCl₃) 4.31 (1H, d, J_H–P23.1 Hz), 7.36 (1H, d, J 3.9 Hz),

7.40–7.83 (25H, m), 8.06 (1H, s); δ_C(CDCl₃, 67.8 MHz, DEPT

136.50, 142.41, 148.77, 177.39 (C᎐O); MS (FAB, 3-nitrobenzyl

᎐

alcohol) 508 (MH^ϩ, 40%), 307 ( 73), 303 (12). HRMS found:

508.1134; calcd. for C₃₀H₂₃O₃NPS: 508.1136 (MH^ϩ).

1

90, DEPT 135) 50.12 (C_quat, J_C᎐P113.4 Hz), 123.68 (ϩ, CH),

124.24 (ϩ, CH), 124.40 (ϩ, CH^᎐), 125.89 (ϩ, CH), 126.45 (ϩ,

1

CH), 127.12 (ϩ, CH), 127.16 (C_quat, J_C–P96.5 Hz), 127.69 (ϩ,

1,4-Bis{5-[(triphenylphosphoranylidene)acetyl]-2-thienyl}benzene

(5n)

CH), 128.12 (ϩ, CH), 128.44 (ϩ, CH), 128.93 (ϩ, CH, J_C–P12.2

Hz), 132.13 (ϩ, CH, J_C–P2.4 Hz), 132.34 (C_quat), 132.92 (C_quat),

133.28 (ϩ, CH J_C–P9.8 Hz), 133.78 (C_quat), 145.79 (C_quat),

A mixture of 3b (240 mg, 0.51 mmol), 1,4-phenylenediboronic

acid (44 mg, 0.27 mmol) and Pd(PPh₃)₄(25 mg, 2.2 × 10^Ϫ2

mmol) in DME (3.5 mL) and 2 M aq. Na₂CO₃(2 mL) was held

at 75 ЊC for 5 h. Thereafter water (5 mL) was added to the

cooled mixture and it was extracted with chloroform (3 ×

10 mL). The combined organic phase was dried over anhydrous

MgSO₄and evaporated in vacuo to give a residue, which was

taken up with ether (15 mL). The precipitate formed was ﬁl-

tered and washed generously with ether and subsequently dried

to give 5n (80 mg, 35%) as a light yellow solid, mp 270–275 ЊC

(decomp., ether); ν_max(KBr)/cm^Ϫ13054, 1544, 1522, 1501, 1480,

1436, 1386, 1103, 879, 731; δ_H(270 MHz, CDCl₃) 4.32 (2H, d,

²J_P–H22.4 Hz), 7.46–7.76 (34H, m), 7.61 (4H, s); MS (FAB,

3-nitrobenzyl alcohol) m/z 847 (MH^ϩ, 1.4%). HRMS found:

847.2020; calcd. for C₅₄H₄₁O₂P₂S₂: 847.2023 (MH^ϩ).

148.01 (C_quat, J_C–P17.1 Hz), 178.24 (C_quat, C᎐O); MS (FAB,

᎐

3-nitrobenzyl alcohol) m/z 513 (MH^ϩ, 100%), 303 (36). HRMS

found: 513.1439; calcd. for C₃₄H₂₆OPS: 513.1442 (MH^ϩ).

5-(o-Tolyl)-2-thienylcarbonylmethylidenetriphenylphosphorane

(5k)

A mixture of 3b (153 mg, 0.33 mmol), o-tolylboronic acid

(88 mg, 0.65 mmol) and Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3mmol) in

DME (3 mL) and 2 M aq. Na₂CO₃(1.3 mL) was held at 75 ЊC

for 6h. Work-up according to general procedure A and column

chromatography on silica gel (ether) gave 5k (88 mg, 56%) as a

pale yellow solid; mp 172 ЊC (ether); ν_max(KBr)/cm^Ϫ13058,

1539, 1517, 1483, 1455, 1436, 1394, 1246, 1181, 1106, 1037, 866,

2102

J. Chem. Soc., Perkin Trans. 1, 2002, 2090–2110

View Article Online

2-Phenylbenzoylmethylidenetriphenylphosphorane (6a)

¹J_C–P90.1 Hz), 128.44 (CH), 128.48 (CH), 128.89 (CH, J_C–P12.2

Hz), 130.77 (CH, J 3.7 Hz), 132.07 (CH, J_C–P2.5 Hz), 133.19

A mixture of 3c (153 mg, 0.33 mmol), phenylboronic acid

(100 mg, 0.65 mmol) and Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3mmol)

in DME (3 mL) and 2 M aq. Na₂CO₃(1.3 mL) was held at

75 ЊC for 10 h. Work-up according to general procedure A and

column chromatography on silica gel (eluant: ether–chloroform

2 : 1) gave 6a (142 mg, 94%) as a colorless oil; ν_max(KBr)/cm^Ϫ1

3054, 2924, 1525, 1481, 1437, 1388, 1187, 1107, 746, 719, 693;

(CH, J_C–P9.7 Hz), 136.71 (C_quat), 140.50 (C_quat, J 14.6 Hz),

2

159.83 (C_quat

,

¹J_C–F(Ϫ)247.8 Hz), 184.33 (C_quat, C᎐O, J_C–P

᎐

2.4 Hz); MS (70 eV) m/z 474 (M^ϩ, 82%), 303 (61), 277 (60),

183 (100). HRMS found: 474.1547; calcd. for C₃₂H₂₄OFP:

474.1549.

δ_C(67.8 MHz, CDCl₃, DEPT 90, DEPT 135) 56.47 (¹J_C᎐P106.0

Hz, CH), 126.76 (CH), 127.26 (CH), 127.19 (C_quat, J_C–P90.2

2-(p-Vinylphenyl)benzoylmethylidenetriphenylphosphorane

(6e)

᎐

1

Hz), 128.20 (J 11.0 Hz, CH), 128.64 (CH), 128.86 (CH), 129.15

(J 12.3 Hz, CH), 129.94 (CH), 130.33 (CH), 132.43 (J 2.4 Hz,

CH), 132.61 (CH), 133.58 (J 9.7 Hz, CH), 140.23 (C_quat), 143.18

A mixture of 3c (153 mg, 0.33 mmol), 4-vinylphenylboronic

acid (97 mg, 0.66 mmol) and Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3

mmol) in DME (3 mL) and 2 M aq. Na₂CO₃(1.3 mL) was held

at 75 ЊC for 5 h. Work-up according to general procedure A and

column chromatography on silica gel (ether) gave 6e (115 mg,

72%) as a colorless solid; ν_max(neat)/cm^Ϫ13054, 1525, 1437,

1387, 1195, 1117, 746, 720, 694; δ_H(270 MHz, CDCl₃) 3.63 (1H,

d, ²J_P–H24.6 Hz), 5.24 (1H, d, ³J 11.5 Hz), 5.74 (1H, d, ³J 17.1

(C_quat), 144.37 (J_C–P15.9 Hz, C_quat), 188.72 (J_C–P3.7 Hz, C_quat

,

C᎐O); MS (FAB) m/z 457 (MH^ϩ, 100%), 303 (24), 279 (37).

᎐

HRMS (FAB) found: 457.1717 (MH^ϩ); calcd. for C₃₂H₂₆OP:

457.1721.

3

2-(p-Methoxyphenyl)benzoylmethylidenetriphenylphosphorane

(6b)

Hz), 6.75 (1H, dd, J 11.5, J 17.1 Hz), 7.27–7.75 (23H, m);

δ_C(67.8 MHz, CDCl₃, DEPT 90, DEPT 135) 56.81 (CH, J_C᎐P

1

106.0 Hz), 113.98 (Ϫ), 126.43 (CH), 127.47 (C_quat, J_C–P90.2

A mixture of 3c (153 mg, 0.33 mmol), p-methoxyphenylboronic

acid (100 mg, 0.66 mmol), Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3mmol)

in 2 M Na₂CO₃(1.3 mL) and DME (3 mL) was held at reﬂux

for 8 h. Thereafter the cooled reaction mixture was worked up

acccording to procedure A. Column chromatography on silica

gel (ether) gave 6b (104 mg, 65%) as a colorless slow-moving oil.

ν_max(neat)/cm^Ϫ11517, 1438, 1387, 1182, 1117, 720, 695; δ_H(270

MHz, CDCl₃) 3.58 (1H, d, ²J_P–H25.4 Hz), 3.73 (3H, s, OCH₃),

6.72 (2H, d, ³J 8.6 Hz), 7.18–7.21 (3H, m), 7.31–7.51 (12H, m),

7.56–7.63 (6H, m); δ_C(67.8 MHz, CDCl₃, DEPT 90, DEPT

135) 55.24 (OCH₃), 158.40 (C_quat); MS (FAB, 3-nitrobenzyl

alcohol) m/z 487 (MH^ϩ, 100%), 303 (21), 279 (89). HRMS

(FAB) found: 487.1830 (MH^ϩ); calcd. for C₃₃H₂₈O₂P: 487.1827.

Hz), 127.69 (CH), 128.66 (CH), 129.00 (CH), 129.33 (CH, J_C–P

12.2 Hz), 129.61 (CH), 130.49 (CH), 132.89 (CH, J_C–P11.0 Hz),

133.95 (CH, J_C–P11.0 Hz), 136.47 (C_quat), 137.70 (CH), 140.26

(C_quat), 143.19 (C_quat), 144.82 (C_quat, J_C–P15.8 Hz), 189.00 (C_quat

,

J_C–P2.4 Hz, C᎐O); MS (FAB, 3-nitrobenzyl alcohol) m/z 483

᎐

(MH^ϩ, 100%), 303 (36), 279 (55). HRMS found: 483.1879

(MH^ϩ); calcd. for C₃₄H₂₈OP: 483.1878.

3-Phenylbenzoylmethylidenetriphenylphosphorane (7a)

A mixture of 3d (76 mg, 0.17 mmol), phenylboronic acid (63 mg,

0.51 mmol), Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3mmol) in DME

(1.5 mL) and 2 M Na₂CO₃(0.6 mL) was reacted at 75 ЊC for

7 h. Column chromatography on silica gel (ether) gave 7a as a

colorless, crystalline solid (63 mg, 81%); mp 216–218 ЊC (ether)

(Found: C, 84.25; H, 5.56. C₃₂H₂₅OP requires C, 84.19; H,

5.52%); ν_max(KBr)/cm^Ϫ13052, 2922, 1522, 1376, 1105, 886, 731,

691; δ_H(270 MHz, CDCl₃) 4.45 (1H, d, ill-resolved), 7.28–7.77

2-(p-Fluorophenyl)benzoylmethylidenetriphenylphosphorane

(6c)

A mixture of 3c (153 mg, 0.33 mmol), p-ﬂuorophenylboronic

acid (93 mg, 0.65 mmol) and Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3

mmol) in DME (3 mL) and 2 M aq. Na₂CO₃(1.3 mL) was

reacted at 75 ЊC for 6 h. Work-up according to general pro-

cedure A and column chromatography on silica gel (eluant:

ether–chloroform 2 : 1) gave 6c (149 mg, 95%) as a colorless oil;

ν_max(neat)/cm^Ϫ13054, 2972, 1512, 1482, 1437, 1387, 1189, 1117,

3

(22H, m), 7.94 (1H, d, J 7.9 Hz), 8.21 (1H, s); δ_C(67.8 MHz,

CDCl₃) 50.98 (CH, ¹J_C᎐P112.3 Hz), 125.84 (CH), 125.97 (CH),

᎐

127.06 (CH), 127.16 (C_quat, ¹J_C–P91.4 Hz), 127.31 (CH), 128.07

(CH), 128.18 (CH), 128.59 (CH), 128.88 (CH, J_C–P12.2 Hz),

132.05 (CH, J_C–P3.6 Hz), 133.20 (CH, J_C–P9.7 Hz), 140.75

750, 720, 694; δ_H(270 MHz, CDCl₃) 3.66 (1H, d, ¹J_C᎐P25.4 Hz),

(C_quat), 141.49 (C_quat), 141.94 (C_quat, J_C–P14.6 Hz), 184.83 (C_quat

,

᎐

3

2

C᎐O, J_C–P3.5 Hz); MS (70 eV) m/z 456 (M^ϩ, 100%), 303

6.93 (2H, dd, J 8.6, J 8.9 Hz), 7.28–7.81 (21H, m); δ_C(67.8

᎐

MHz, DEPT 90, DEPT 135) 55.75 (¹J_C᎐P106.0 Hz), 114.40 (ϩ,

(Ph₃PCHCO^ϩ, 95), 277 (39), 183 (51), 149 (82). HRMS found:

456.1646; calcd. for C₃₂H₂₅OP: 456.1643.

᎐

1

J 20.7 Hz), 126.72 (C_quat, J_C–P90.2 Hz), 126.88 (CH), 129.79

(CH), 132.03 (CH, J 4.9 Hz), 133.10 (CH, J 9.7 Hz), 138.63

(C_quat), 144.16 (C_quat, J 15.9 Hz), 188.38 (C_quat, J 3.7 Hz, C᎐O);

3-(p-Methoxyphenyl)benzoylmethylidenetriphenylphosphorane

(7b)

᎐

MS (FAB, 3-nitrobenzyl alcohol) m/z 475 (MH^ϩ, 100%), 303

(24), 279 (91). HRMS found: 475.1624 (MH^ϩ); calcd. for

C₃₂H₂₅OFP: 475.1627.

A mixture of 3d (153 mg, 0.33 mmol), p-methoxyphenylboronic

acid (100 mg, 0.66 mmol), Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3mmol)

in 2 M Na₂CO₃(1.3 mL) and DME (3 mL) was held at reﬂux

for 5 h. Thereafter the cooled reaction mixture was worked up

acccording to procedure A. Column chromatography on silica

gel (ether) gave 7b (152 mg, 95%) as colorless needles, mp 136–

138 ЊC (ether); ν_max(KBr)/cm^Ϫ13054, 1609, 1513, 1438, 1375,

1246, 1107, 693; δ_H(270 MHz, CDCl₃) 3.84 (3H, s, OCH₃), 4.47

(1H, d, ²J_P–H24.4 Hz), 6.95 (2H, d, ³J 7.9 Hz), 7.37–7.61 (15H,

m), 7.71 (2H, d, ³J 8.2 Hz), 7.76 (2H, d, ³J 7.9 Hz), 7.90 (1H, d,

³J 7.6 Hz), 8.17 (1H, s); δ_C(67.9 MHz, CDCl₃, DEPT 90, DEPT

135) 50.8 (CH, ¹J_C–P111.6 Hz), 55.35 (ϩ, OCH₃), 114.12 (CH),

125.41 (CH), 127.27 (¹J_C–P91.3 Hz, C_quat), 127.65 (CH), 128.10

(CH), 128.30 (CH), 128.88 (CH, J 12.2 Hz), 132.02 (CH, J 2.4

Hz), 133.22 (CH, J 9.7 Hz), 134.11 (C_quat), 140.36 (C_quat), 141.81

2-(o-Fluorophenyl)benzoylmethylidenetriphenylphosphorane

(6d)

A mixture of 3c (263 mg, 0.57 mmol), o-ﬂuorophenylboronic

acid (136 mg, 0.97 mmol) and Pd(PPh₃)₄(28 mg, 2.4 × 10^Ϫ2

mmol) in DME (3 mL) and 2 M aq. Na₂CO₃(2.3 mL) was held

at 75 ЊC for 6 h. Work-up according to procedure A and column

chromatography on silica gel (ether ethyl acetate–ether 1 : 9)

gave 6d (149 mg, 55%) as colorless needles (Found: C, 81.13; H,

5.18. C₃₂H₂₄OFP requires C, 81.00; H, 5.10%); ν_max(KBr)/cm^Ϫ1

3048, 1581, 1510, 1481, 1450, 1436, 1408, 1385, 1190, 1103, 881,

756, 747, 715, 691; δ_H(270 MHz, CDCl₃) 4.48 (1H, d, ²J_P–H24.4

Hz), 7.09–7.31 (4H, m), 7.43–7.60 (11H, m), 7.69–7.78 (6H,

3

m), 8.05 (2H, d, J 8.8 Hz); δ_C(67.8 MHz, CDCl₃, DEPT 90,

(C_quat, J 16.2 Hz), 159.11 (C_quat), 185.01 (C_quat, C᎐O); MS

᎐

DEPT 135) 50.92 (CH, J_C᎐P112.3 Hz), 116.07 (CH, J_C–F

(70 eV) m/z 486 (M^ϩ, 97%), 303 (100), 277 (35), 183 (50).

1

2

23.2 Hz), 124.28 (CH, J 3.7^᎐Hz), 127.04 (CH), 127.08 (C_quat

,

HRMS found: 486.1747; calcd. for C₃₃H₂₇O₂P: 486.1749.

J. Chem. Soc., Perkin Trans. 1, 2002, 2090–2110

2103

View Article Online

3-(2,4-Diﬂuorophenyl)benzoylmethylidenetriphenylphosphorane

(7c)

and chloroform (2 × 15 mL). The combined organic phase

was washed with water, dried over MgSO₄and concentrated

in vacuo. Ether (20 mL) was added to the residue and the

precipitate formed was ﬁltered oﬀ and washed with cold ether

to give 4a (233 mg, 49%).

A mixture of 3d (153 mg, 0.33 mmol), 2,4-diﬂuorophenyl-

boronic acid (104 mg, 0.66 mmol) and Pd(PPh₃)₄(10 mg, 9.0 ×

10^Ϫ3mmol) in DME (3 mL) and 2 M aq. Na₂CO₃(1.3 mL) was

held at 75 ЊC for 5 h. Work-up according to general procedure

A and column chromatography on silica gel (ether) gave 7c

(134 mg, 82%) as a colorless solid; R_f0.40; ν_max(KBr)/cm^Ϫ1

3048, 2924, 1620, 1597, 1526, 1506, 1481, 1438, 1377, 1103, 882,

868, 848, 754, 745; δ_H(270 MHz, CDCl₃) 4.46 (1H, br s),

6.89 (2H, m), 7.39–7.76 (18H, m), 7.96 (1H, d, ³J 7.9 Hz), 8.08

(1H, s); MS (70 eV) m/z 492 (M^ϩ, 100%), 303 (Ph₃PCHCO^ϩ,

84), 262 (76), 183 (77); MS (70 eV) m/z (%) 492 (M^ϩ, 100), 303

(Ph₃PCHCO^ϩ, 84), 262 (76), 183 (77). HRMS found: 492.1456;

calcd. for C₃₂H₂₃OF₂P: 492.1455.

Biphenyl-4-ylcarbonylmethylidenetriphenylphosphorane (4b)

A mixture of 2a (527 mg, 0.97 mmol), phenylboronic acid

(238 mg, 1.95 mmol) and Pd(PPh₃)₄(27 mg, 2.3 × 10^Ϫ2mmol)

in DME (5 mL) and 2 M aq. Na₂CO₃(3.7 mL) was treated

according to procedure B (5 h, 75 ЊC). Column chromatography

on silica gel (ether) yielded 4b (286 mg, 64%).

4-(p-Fluorophenyl)benzoylmethylidenetriphenylphosphorane (4d)

A mixture of 2a (268 mg, 0.5 mmol), p-ﬂuorophenylboronic

acid (140 mg, 1.0 mmol) and Pd(PPh₃)₄(12.5 mg, 1.1 mmol) in

DME (2.5 mL) and 2 M aq. Na₂CO₃(1.85 mL) was treated

according to procedure B (5 h, 75 ЊC). Column chromatography

on silica gel (ether ether–ethyl acetate 95 : 5) gave 4d (146 mg,

62%).

3-(m-Nitrophenyl)benzoylmethylidenetriphenylphosphorane (7d)

A mixture of 3d (153 mg, 0.33 mmol), m-nitrophenylboronic

acid (110 mg, 0.66 mmol) and Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3

mmol) in DME (3 mL) and 2 M aq. Na₂CO₃(1.3 mL) was held

at 75 ЊC for 5 h. Work-up according to general procedure A and

column chromatography on silica gel (ether) gave 7d (148 mg,

89%) as a pale yellow solid, mp 78–81 ЊC (ether–hexane 1 : 1)

(Found: C, 76.31; H, 5.26; N, 2.62. C₃₂H₂₄O₃NP requires C,

76.64; H, 4.82; N, 2.79%); ν_max(KBr)/cm^Ϫ13058, 2924, 1522,

1438, 1381, 1351, 1107, 909, 880, 731; δ_H(270 MHz, CDCl₃)

p-(2-Thienyl)benzoylmethylidenetriphenylphosphorane (4j)

A mixture of 2a (527 mg, 0.97 mmol), 2-thienylboronic acid

(250 mg, 1.95 mmol) and Pd(PPh₃)₄(27 mg, 2.3 × 10^Ϫ2mmol)

in DME (5 mL) and 2 M aq. Na₂CO₃(3.7 mL) was treated

according to procedure B (7 h, 75 ЊC). Column chromatography

on silica gel (ether) yielded 4j (190 mg, 42%).

2

4.50 (1H, d, J_H–P23.1 Hz), 7.48–7.78 (18H, m), 8.01 (2H, m),

8.17 (1H, d, ³J 6.9 Hz), 8.26 (1H, s), 8.51 (1H, s); δ_C(67.8 MHz,

1

CDCl₃, DEPT 90, DEPT 135) 51.88 (CH, J_C᎐P112.3 Hz),

122.14 (CH), 122.36 (CH), 126.18 (CH), 126.65 ^᎐(CH), 127.65

(CH), 128.00 (C_quat), 128.39 (CH), 128.84 (CH), 129.38 (CH,

J_C–P12.2 Hz), 129.96 (CH), 132.59 (CH, J_C–P2.4 Hz), 133.61

(CH, J_C–P11.0 Hz), 138.65 (C_quat), 142.75 (C_quat, J_C–P14.6 Hz),

4-(p-Triﬂuoromethylphenyl)benzoylmethylidenetriphenylphos-

phorane (4k)

A mixture of 2a (527 mg, 0.97 mmol), p-triﬂuorophenylboronic

acid (185 mg, 0.97 mmol) and Pd(PPh₃)₄(27 mg, 2.3 × 10^Ϫ2

mmol) in DME (7.0 mL) and 2 M aq. Na₂CO₃(4.7 mL) was

treated according to procedure B (12h, 75 ЊC). Column chroma-

tography on silica gel (ether) gave 4k (276 mg, 54%).

143.56 (C_quat), 149.15 (C_quat), 184.47 (²J_C–P2.4 Hz, C᎐O); MS

᎐

(FAB, 3-nitrobenzyl alcohol) m/z 502 (MH^ϩ, 100%), 303 (Ph₃-

PCHCO^ϩ, 45). HRMS found: 501.1492; calcd. for C₃₂H₂₄O₃-

NP: 501.1494.

4-(2-Naphthyl)benzoylmethylidenetriphenylphosphorane (4l)

3-(p-Vinylphenyl)benzoylmethylidenetriphenylphosphorane (7e)

A mixture of 2a (527 mg, 0.97 mmol), 2-naphthylboronic acid

(166 mg, 0.97 mmol) and Pd(PPh₃)₄(27 mg, 2.3 × 10^Ϫ2mmol) in

DME (7.0 mL) and 2 M aq. Na₂CO₃(4.7 mL) was treated

according to procedure B (8 h, 75 ЊC). Column chromatography

on silica gel (ether) gave 4l (272 mg, 55%).

A mixture of 3d (153 mg, 0.33 mmol), 4-vinylphenylboronic

acid (97 mg, 0.66 mmol) and Pd(PPh₃)₄(10 mg, 9.0 × 10^Ϫ3

mmol) in DME (3 mL) and 2 M aq. Na₂CO₃(1.3 mL) was held

at 75 ЊC for 5 h. Work-up according to general procedure A and

column chromatography on silica gel (ether) gave 7e (112 mg,

70%) as a pale yellow solid (Found: C, 84.67; H, 5.75. C₃₄H₂₇OP

requires C, 84.62; H, 5.64%); ν_max(KBr)/cm^Ϫ13048, 2924, 2852,

1523, 1511, 1479, 1435, 1375, 1105, 888, 756, 729, 693; δ_H(270

p-(2-Phenylethenyl)benzoylmethylidenephosphorane (8a)

Method A. A mixture of 3a (500 mg, 1.09 mmol), styrene

(0.19 mL, 170 mg, 1.64 mmol), triethylamine (0.18 mL, 132 mg,

1.31 mmol), palladium acetate (24 mg, 0.11 mmol) and tri-

phenylphosphine (71 mg, 0.27 mmol) in N,N-dimethylform-

amide (2 mL) was heated at 100 ЊC for 24 h. Thereafter the

cooled solution was diluted with water and extracted with

dichloromethane. The organic phase was washed with water,

dried over anhydrous MgSO₄and concentrated in vacuo.

Chromatography on silica gel (eluant: ether) yielded 8a (32 mg,

6%) as a pale yellow powder (ether), mp 208–210 ЊC (ether)

(Found: C, 83.83; H, 5.69. C₃₄H₂₇OPؒ0.25H₂O requires C,

83.59; H, 5.56%); ν_max(KBr)/cm^Ϫ13050, 1519, 1481, 1437, 1410,

1387, 1103, 880, 746, 715, 693; δ_H(270 MHz, CDCl₃) 4.45

(d, 1H, ²J_H–P24.5 Hz), 7.14 (s, 2H), 7.32–7.76 (m, 22H), 7.96 (d,

2

3

MHz, CDCl₃) 4.48 (1H, d, J_P–H24.1 Hz), 5.25 (1H, d, J 10.9

Hz), 5.77 (1H, d, ³J 17.5 Hz), 6.74 (1H, dd, ³J 10.9, ³J 17.5 Hz),

7.39–7.65 (17H, m), 7.73 (2H, d, ³J 7.9 Hz), 7.76 (2H, d, ³J 7.9

Hz), 7.93 (1H, d, ³J 7.6 Hz), 8.23 (1H, s); δ_C(67.9 MHz, CDCl₃,

DEPT 90, DEPT 135) 50.88 (CH,J_C᎐P108.8 Hz), 113.57 (Ϫ),

125.61 (CH), 126.04 (CH), 126.51 (^᎐CH), 127.17 (C_quat, J_C–P

1

90.2 Hz), 127.35 (CH), 127.89 (CH), 128.16 (CH), 128.86 (CH,

J_C–P12.2 Hz), 132.02 (CH, J_C–P2.4 Hz), 133.21 (CH, J_C–P9.7

Hz), 136.49 (C_quat), 136.59 (CH), 140.25 (C_quat), 140.86 (C_quat),

142.01 (C_quat, J_C–P14.6 Hz), 184.85 (C_quat, J_C–P2.4 Hz, C᎐O);

᎐

MS (70 eV) m/z 482 (M^ϩ, 19%), 303 (25), 262 (50), 178 (57).

HRMS found: 482.1801; calcd. for C₃₄H₂₇OP: 482.1800.

3

1

2H, J 8.6 Hz); δ_C(67.8 MHz, CDCl₃) 50.91 (CH, J_C᎐P112.1

Hz), 125.95 (ϩ, CH), 126.52 (ϩ, CH), 127.03 (C_quat, J_C–P91.3

Hz), 127.35 (ϩ, CH), 127.58 (ϩ, CH), 128.55 (ϩ, CH), 128.64

(ϩ, CH), 128.84 (ϩ, CH), 128.87 (ϩ, CH, J_C–P12.1 Hz), 132.06

(ϩ, CH, J_C–P2.4 Hz), 133.16 (CH, J_C–P10.9 Hz), 137.37 (C_quat),

4Ј-Methoxybiphenyl-4-ylcarbonylmethylidenetriphenylphos-

phorane (4a)—general procedure B

A mixture of p-bromobenzoylmethylenephosphonium bromide

2a (527 mg, 0.97 mmol), p-methoxyphenylboronic acid

(297 mg, 1.95 mmol) and Pd(PPh₃)₄(27 mg, 2.3 × 10^Ϫ2mmol) in

DME (7 mL) and 2 M aq. Na₂CO₃(4.7 mL) was heated for 5 h

at 75 ЊC. After the reaction mixture had cooled, water (15 mL)

was added and the mixture was extracted with ether (10 mL)

138.27 (C_quat), 140.50 (C_quat, J_C–P14.6 Hz), 184.28 (C᎐O, C

,

᎐

quat

²J_C–P2.4 Hz). MS (FAB, 3-nitrobenzyl alcohol) m/z 483 (MH^ϩ,

51%). HRMS found: 483.1877; calcd. for C₃₄H₂₈OP: 483.1878

(MH^ϩ).

2104

J. Chem. Soc., Perkin Trans. 1, 2002, 2090–2110

View Article Online

Method B. A mixture of 3e (273 mg, 0.54 mmol), styrene

(0.1 mL, 84 mg, 0.81 mmol), triethylamine (0.09 mL, 65 mg,

0.65 mmol), palladium acetate (12 mg, 0.054 mmol) and tri-

phenylphosphine (35 mg, 0.135 mmol) in N,N-dimethyl-

formamide (1 mL) was heated at 100 ЊC for 2 h. Thereafter

the cooled solution was diluted with water, dried over

anhydrous MgSO₄and concentrated in vacuo. Chromatography

on silica gel (eluant: ether–ethyl acetate 1 : 1) yielded 8a

(117 mg, 45%).

p-(2-Methoxycarbonylethenyl)benzoylmethylidenephosphorane

(8c)

Method A. A mixture of 3a (500 mg, 1.09 mmol), methyl

acrylate (0.15 mL, 141 mg, 1.64 mmol), triethylamine (0.18 mL,

132 mg, 1.31 mmol), palladium acetate (24 mg, 0.11 mmol) and

triphenylphosphine (71 mg, 0.27 mmol) in N,N-dimethyl-

formamide (2 mL) was heated at 100 ЊC for 24 h. Thereafter the

cooled solution was diluted with water and extracted with

dichloromethane. The organic phase was washed with water,

dried over anhydrous MgSO₄and concentrated in vacuo.

Chromatography on silica gel (eluant: chloroform–ethyl acetate

5 : 1–3 : 1) yielded 8c (193 mg, 38%) as an orange powder

(ether); mp 198–199 ЊC (ether) (Found: C, 76.69; H, 5.49.

C₃₀H₂₅0₃Pؒ0.25H₂O requires C, 76.82; H, 5.37%); ν_max(KBr)/

cm^Ϫ13042, 1712, 1633, 1574, 1518, 1480, 1437, 1408, 1388,

1312, 1203, 1171, 1104, 881, 840, 747, 716, 694; δ_H(270 MHz,

Method C. A mixture of 3e (108 mg, 0.21[5] mmol), styrene

(60 mg, 0.58 mmol), tetrabutylammonium chloride (71 mg,

0.25[5] mmol), NaHCO₃(44 mg, 0.52 mmol), and palladium()

acetate (18 mg, 0.08 mmol) in chloroform (1.5 mL) was stirred

at rt for 72 h. Thereafter water (5 mL) was added and the

mixture was extracted with chloroform (2 × 15 mL). The com-

bined organic phase was dried over anhydrous MgSO₄and

concentrated in vacuo. Column chromatography of the residue

on silica gel (ether) gave 8a (78 mg, 75%).

1

CDCl₃) 3.80 (3H, s, OCH₃), 4.45 (1H, d, J_H–P24.1 Hz), 6.46

(1H, d, ³J 16.2 Hz, olef. H), 7.46–7.58 (11H, m), 7.60–7.75 (7H,

m), 7.98 (2H, d, Ar-H); δ_C(67.8 MHz, DEPT 90, DEPT 135)

51.65 (ϩ, COOCH₃), 51.70 (ϩ, CH, ¹J_C᎐P112.2 Hz), 117.79 (ϩ,

᎐

(E )-p-(2-Cyanoethenyl)benzoylmethylidenetriphenylphosphorane

(8b)

1

CH), 126.79 (C_quat, J_C–P90.1 Hz), 127.46 (ϩ, CH), 127.64 (ϩ,

CH), 128.91 (ϩ, CH, J_C–P12.2 Hz), 132.15 (ϩ, CH, J_C–P2.4

Method 1. A mixture of p-bromobenzoylmethylidenetri-

phenylphosphorane (3a) (250 mg, 0.54 mmol), acrylonitrile

(0.05 mL, 43 mg, 0.82 mmol), triethylamine (0.09 mL, 65 mg,

0.65 mmol), palladium acetate (12 mg, 0.054 mmol) and tri-

phenylphosphine (35 mg, 0.135 mmol) in N,N-dimethylform-

amide (1 mL) was heated at 90 ЊC for 15 h. Thereafter the

cooled solution was diluted with water and extracted with

dichloromethane. The organic phase was washed with water,

dried over magnesium sulfate and concentrated in vacuo.

Chromatography on silica gel (eluant: ether–ethyl acetate 1 : 0–

1 : 1) yielded 8b (42 mg, 18%) as an orange powder (ether),

mp 209–210 ЊC (ether) (Found: C, 80.28; H, 5.21; N, 3.21.

C₂₉H₂₂ONPؒ0.25H₂O requires C, 79.89; H, 5.20; N, 3.21%); ν_max

(KBr)/cm^Ϫ13008, 2212, 1614, 1573, 1495, 1478, 1436, 1412,

1394, 1310, 1211, 1179, 1105, 1071, 1014, 997, 972, 883, 824,

752, 715, 693; δ_H(270 MHz, CDCl₃) 4.38 (1H, d, ²J_H–P23.1 Hz),

5.81 (1H, d, J 16.7 Hz), 7.29–7.68 (18H, m), 7.91 (2H, d, ³J 7.3

Hz), 133.14 (ϩ, CH, J_C–P9.9 Hz), 135.11 (C_quat), 143.07 (C_quat

,

J_C–P14.6 Hz), 144.69 (ϩ, CH), 167.49 (C_quat, C᎐O, COOCH );

᎐

3

MS (70 eV) m/z 464 (M^ϩ, 100%), 435 (M^ϩϪ CHO, 22), 303

(M^ϩϪ CH COOCH᎐CHPh, 73). HRMS found: 464.1539;

᎐

3

calcd. for C₃₀H₂₅O₃P: 464.1541.

Method B—general procedure D. A mixture of 3e (166 mg,

0.33 mmol), methyl acrylate (57 mg, 0.66 mmol), solid Na-

HCO₃(68 mg, 0.8 mmol), benzyltrimethylammonium chloride

(61 mg, 0.33 mmol) and Pd(OAc)₂(4.4 mg, 0.02 mmol) in dry

DMF (1 mL) was stirred at rt and under an inert atmosphere

for 60 h. Then water (5 mL) was added and the mixture was

extracted with chloroform (3 × 10 mL). The organic phase was

washed with water (3 × 10 mL), dried over anhydrous MgSO₄

and concentrated in vacuo. The residue was subjected to column

chromatography (ether) to give 8c (147 mg, 96%).

1

(E )-p-[2-(Morpholinocarbonyl)ethenyl]benzoylmethylidenetri-

phenylphosphorane (8d)

Hz); δ_C(67.8 MHz, CDCl₃) 52.09 (CH, J_C᎐P110.9 Hz), 96.10

(CH), 118.29 (CN), 126.59 (C_quat, J_C–P91.4^᎐Hz), 126.92 (CH),

1

127.60 (CH), 128.93 (CH, J_C–P12.2 Hz), 132.20 (CH, J_C–P2.4

A mixture of 3e (108 mg, 0.215 mmol), N-morpholinylacryl-

amide (75 mg, 0.53 mmol), solid NaHCO₃(44 mg, 0.5 mmol),

benzyltrimethylammonium chloride (40 mg, 0.22 mmol) and

Pd(OAc)₂(4.0 mg, 0.02 mmol) in dry DMF (1 mL) is treated

according to procedure D (reaction time: 40 h). Chroma-

tography on silica gel (eluant: ether–ethyl acetate) gives 8d

(71 mg, 64%) as an oﬀ-white solid; mp 236–238 ЊC (ether)

(Found: C, 74.55; H, 5.86; N, 2.58. C₃₃H₃₀O₃NPؒ0.75H₂O

requires C, 74.35; H, 5.95; N, 2.63%); ν_max(KBr)/cm^Ϫ13054,

2964, 2850, 1651, 1640, 1605, 1572, 1510, 1500, 1438, 1409,

1389, 1228, 1108, 883, 846, 748; δ_H(270 MHz, CDCl₃) 3.73 (8H,

br s), 4.44 (1H, d, ²J_P–H24.1 Hz), 6.86 (1H, d, ³J 15.2 Hz), 7.45–

Hz), 133.08 (CH, J_C–P9.8 Hz), 134.07 (C_quat), 143.92 (C_quat, J_C–P

2

14.6 Hz), 150.37 (CH), 183.12 (C᎐O, J

3.7 Hz); MS (EI,

᎐

C–P

70 eV) m/z 431 (M^ϩ, 100%), 402 (M^ϩϪ CHO, 21), 303 ([M^ϩϪ

NC-CH᎐CH-Ph], 70); HRMS found: 432.1521; calcd. for

᎐

C₂₉H₂₃NOP: 432.1517 (MH^ϩ, FAB).

Method 2. A mixture of p-iodobenzoylmethylidenetriphenyl-

phosphorane (3e) (273 mg, 0.54 mmol), acrylonitrile (0.05 mL,

43 mg, 0.82 mmol), triethylamine (0.09 mL, 65 mg, 0.65 mmol),

palladium acetate (12 mg, 0.054 mmol) and triphenylphosphine

(35 mg, 0.135 mmol) in N,N-dimethylformamide (1 mL) was

heated at 90 ЊC for 15 h. Thereafter the cooled solution was

diluted with water and extracted with dichloromethane. The

organic phase was washed with water, dried over magnesium

sulfate and concentrated in vacuo. Chromatography on silica gel

(eluant: ether–ethyl acetate 1 : 1) yielded 8b (58 mg, 25%) as an

orange powder (ether).

3

7.75 (18H, m), 7.96 (2H, d, J 8.2 Hz); δ_C(67.8 MHz, CDCl₃,

DEPT 90, DEPT 135) 42.60 (Ϫ, very broad), 46.50 (Ϫ, very

1

broad), 51.65 (ϩ, CH, J_C᎐P112.3 Hz), 66.87 (Ϫ, 2C), 116.53

1

(ϩ, CH), 126.82 (C_quat, J_C–P91.5 Hz), 127.35 (ϩ, CH), 127.40

(ϩ, CH), 128.91 (ϩ, CH, J_C–P12.2 Hz), 132.15 (ϩ, CH, J_C–P

1.6 Hz), 133.14 (ϩ, CH, J_C–P9.7 Hz), 135.90 (C_quat), 142.82

(C_quat), 143.02 (ϩ, CH), 165.64 (C_quat, CONR₂), 183.76 (C_quat

᎐

,

Method 3. A mixture of p-iodobenzoylmethylidenetriphenyl-

phosphorane (3e) (108 mg, 0.21 mmol), acrylonitrile (0.05 mL,

43 mg, 0.82 mmol), benzyltrimethylammonium chloride

(40 mg, 0.22 mmol), solid NaHCO₃(40 mg, 0.5 mmol), Pd-

(OAc)₂(9.0 mg, 0.041 mmol) in DMF (1 mL) was stirred at

rt for 60 h. Thereafter, the mixture was poured into water

and extracted with CHCl₃(3 × 15 mL). The organic phase was

washed with water (3 × 10 mL), dried over anhydrous MgSO₄

and concentrated in vacuo. Column chromatography of the

residue on silica gel (ether) gave 8b (50 mg, 55%).

C᎐O); MS (FAB, 3-nitrobenzyl alcohol) m/z 520 (MH^ϩ, 15%),

307 (31), 154 (100). HRMS (FAB, 3-nitrobenzyl alcohol) found:

520.2045; calcd. for C₃₃H₃₁O₃NP: 520.2042 (MH^ϩ).

p-(Phenylethynyl)benzoylmethylidenetriphenylphosphorane (9a)

In an oven-dried ﬂask held under argon was placed p-iodo-

benzoylmethylidenetriphenylphosphorane (3e) (500 mg,

0.99 mmol), dry diisopropylamine (3 mL), dry toluene (1.9 mL)

and Pd(PPh₃)₄(34 mg, 2.9 × 10^Ϫ2mmol). The reaction mixture

J. Chem. Soc., Perkin Trans. 1, 2002, 2090–2110

2105

View Article Online

was heated to 60 ЊC, and phenylacetylene (0.11 mL, 101 mg,

0.99 mmol) and CuI (4 mg, 2.1 × 10^Ϫ2mmol) were added. The

reaction was stirred under argon at 60 ЊC for 13 h. The ﬂask was

allowed to cool to room temperature, and diethyl ether (25 mL)

was added. The mixture was washed with water, and saturated

aqueous NaCl and dried over magnesium sulfate. The solvent

was concentrated in vacuo. Chromatography on silica gel

(eluant: ether–ethyl acetate 1 : 1) yielded 9a (209 mg, 44%) as

yellow powder (ether), mp 222–223 ЊC (ether) (Found: C, 84.98;

H, 5.24. C₃₄H₂₅OP requires C, 85.21; H, 5.27%); ν_max(KBr)/

cm^Ϫ13056, 1565, 1516, 1482, 1438, 1403, 1387, 1188, 1104,

1079, 1015, 998, 876, 853, 753, 718, 689; δ_H(270 MHz, CDCl₃)

3-nitrobenzyl alcohol) m/z 526 (MH^ϩ, 46%). HRMS (FAB, 3-

nitrobenzyl alcohol) found: 526.1577; calcd. for C₃₄H₂₅O₃NP:

526.1572 (MH^ϩ).

p-(p-Amidophenylethynyl)benzoylmethylidenetriphenylphos-

phorane (9d)

A mixture of p-iodobenzoylmethylidenetriphenylphosphorane

(3e) (100 mg, 0.2 mmol), dry isopropylamine (0.6 mL) and

Pd(PPh₃)₄(7 mg, 3mol%, 6.3 µmol) in dry toluene (0.4 mL) was

heated at 60 ЊC under argon, and p-amidophenylacetylene

(29 mg, 0.2 mmol) and CuI (0.3 mg, 2 mol%, 1.5 µmol) were

added. The reaction mixture was stirred at 60 ЊC for 13 h. Then

it was cooled to rt and ether (10 mL) was added. The mixture

was washed with water (5 mL), sat. aq. NaCl solution (5 mL)

and dried over anhydrous MgSO₄. The solvent was evaporated

in vacuo and the residue was subjected to column chroma-

tography on silica gel (ethyl acetate) to give 9d (49 mg, 47%) as a

pale yellow powder, mp 295–296 ЊC (ethyl acetate); R_f0.11

(ethyl acetate); ν_max(KBr)/cm^Ϫ13300, 3166, 1737, 1680, 1609,

1564, 1437, 1238, 1108, 875, 750, 716, 691; δ_H(270 MHz,

2

4.44 (1H, d, J_H–P24.1 Hz), 7.28–7.83 (22H, m), 7.95 (d, 2H,

1

³J 8.3 Hz); δ_C(67.8 MHz, CDCl₃) 51.38 (CH, J_C᎐P110.9 Hz),

᎐

89.77 (C_quat), 90.19 (C_quat), 123.32 (C_quat), 123.97 (C_quat), 126.85

1

(C_quat, J_C–P91.4 Hz), 126.92 (CH), 128.19 (CH), 128.30 (CH),

128.91 (CH, J_C–P12.1 Hz), 131.07 (CH), 131.59 (C_quat), 132.13

(CH, J_C–P2.4 Hz), 133.13 (CH, J_C–P9.8 Hz), 140.95 (C_quat, J_C–P

2

14.6 Hz), 183.79 (C᎐O, J 2.4 Hz); MS (EI, 70 eV) m/z 480

᎐

C–P

(M^ϩ, 100%), 451 (M^ϩϪ CHO, 25), 303 ([M^ϩϪ Ph-C᎐C-Ph],

᎐

74). HRMS (FAB, 3-nitrobenzyl alcohol) found: 481.1714

2

(MH^ϩ); calcd. for C₃₄H₂₆OP: 481.1721.

DMSO-d₆) 4.59 (1H, d, J_H–P24.1 Hz), 7.47–8.07 (25H, m);

δ_CNMR (67.8 MHz, DMSO-d₆, DEPT 135, DEPT 90) 49.68

(CH, ¹J_C᎐P111.3 Hz), 89.72 (C_quat), 91.25 (C_quat), 122.51 (C_quat),

p-(4-Cyanophenylethynyl)benzoylmethylidenetriphenylphos-

phorane (9b)

᎐

124.90 (C_quat), 126.40 (C_quat, J_C–P91.4 Hz), 126.88 (CH), 127.74

(CH), 128.96 (CH, J_C–P12.2 Hz), 130.91 (CH), 131.14 (CH),

132.27 (CH), 132.69 (CH, J_C–P11.0 Hz), 134.00 (C_quat), 140.91

p-Iodobenzoylmethylidenetriphenylphosphorane (3e) (40 mg,

0.08 mmol), p-cyanophenylacetylene (10 mg, 0.08 mmol),

Pd(PPh₃)₄(3 mg, 2.4 × 10^Ϫ6mol, 3 mol%) and CuI (0.3 mg,

1.6 × 10^–6mol, 2 mol%) in dry diisopropylamine (0.24 mL) and

dry toluene (0.15 mL) were reacted (13 h, 60 ЊC, argon) and

worked up as described above. The reaction mixture was puri-

ﬁed by TLC chromatography (ether ether–ethyl acetate 1 : 1)

to give 9b (20 mg, 50%) as a pale yellow solid; mp 277–278 ЊC

(ether); R_f0.54 (ether–ethyl acetate 1 : 1); ν_max(KBr)/cm^Ϫ13050,

2220, 1603, 1565, 1507, 1436, 1404, 1385, 1107, 886, 690; δ_H

(270 MHz, CDCl₃) 4.46 (1H, d, ²J_P–H23.1 Hz), 7.45–7.76 (21H,

(C_quat, J_C–P14.6 Hz), 166.97 (C_quat, C᎐O), 181.47 (C , C᎐O);

᎐

quat

MS (FAB, 3-nitrobenyzl alcohol) m/z 524 (MH^ϩ, 64%); HRMS

found: 524.1779; calcd. for C₃₅H₂₇NO₂P: 524.1777 (MH^ϩ).

5-(4-Cyanophenylethynyl)-2-thienoylmethylidenetriphenyl-

phosphorane (9e)

A mixture of 5-bromo-2-thienoylmethylidenetriphenylphos-

phorane (3b) (70 mg, 0.15 mmol), dry isopropylamine (0.5 mL)

and Pd(PPh₃)₄(5 mg, 4.5 mmol) was heated at 60 ЊC under

argon, and p-cyanophenylacetylene (19 mg, 0.15 mmol) and

CuI (0.6 mg, 3.0 mmol) were added. The reaction mixture

was stirred at 60 ЊC for 4 h. Then it was cooled to rt and ether

(10 mL) was added and the phases were separated. The organic

phase was washed with sat. aq. NaCl (5 mL) and dried over

anhydrous MgSO₄. The solvent was evaporated in vacuo and

the residue was subjected to column chromatography on silica

gel (ether) to give 9e (35 mg, 46%) as yellow needles, mp 240–

242 ЊC; R_f0.18 (ether); ν_max(KBr)/cm^Ϫ13054, 2224, 2194, 1601,

1519, 1436, 1385, 1104, 867, 838, 744, 729; δ_H(270 MHz,

CDCl₃) 4.30 (1H, d, ²J_H–P22.4 Hz), 7.22 (1H, d, ³J 3.6 Hz), 7.41

3

m), 7.97 (2H, d, J 8.2 Hz); δ_C(67.8 MHz, DEPT 90, DEPT

135) 51.93 (CH, ¹J_C᎐P88.52 (C_quat), 94.23 (C_quat), 111.32 (C_quat),

᎐

118.60 (C_quat), 122.84 (C_quat), 126.69 (C_quat

,

¹J_C–P91.4 Hz),

127.06 (CH), 128.33 (C_quat), 128.96 (CH, J_C–P12.1 Hz), 131.34

(CH), 132.14 (CH, J_C–P13.5 Hz), 132.19 (CH), 133.13 (CH, J_C–P

9.8 Hz), 141.78 (C_quat, J_C–P14.6 Hz), 183.50 (C_quat, ²J_C–P2.4 Hz,

C᎐O); MS (FAB, 3-nitrobenzyl alcohol) m/z 506 (MH^ϩ, 100%),

᎐

303 (29). HRMS (FAB, 3-nitrobenzyl alcohol) found: 506.1672

(MH^ϩ); calcd. for C₃₅H₂₅ONP: 506.1674.

p-(4-Nitrophenylethynyl)benzoylmethylidenetriphenylphos-

phorane (9c)

3

(1H, d, J 3.6 Hz), 7.45–7.74 (19H, m); δ_C(67.8 MHz, CDCl₃,

1

DEPT 90, DEPT 135) 51.52 (ϩ, CH, J_C᎐P112.1 Hz), 88.16

p-Iodobenzoylmethylidenetriphenylphosphorane (3e) (500 mg,

0.99 mmol), p-nitrophenylacetylene (146 mg, 0.99 mmol),

Pd(PPh₃)₄(34 mg, 2.72 × 10^Ϫ2mmol, 3 mol%), CuI (4 mg,

2.13 × 10^Ϫ2mmol, 2 mol%) in dry diisoproylamine (3.0 mL)

and dry toluene (1.9 mL) were reacted (13 h, 60 ЊC, argon).

After the reaction had cooled to rt, chloroform (25 mL) was

added, the mixture was washed with water (2 × 15 mL) and sat.

aq. NaCl (1 × 15 mL). The organic phase was dried over

anhydrous MgSO₄. The solvent was removed in vacuo. The resi-

due was washed with ether (20 mL) and yielded 9c (518 mg,

99%) as a pale yellow powder; mp 258–259 ЊC (ether); R_f0.18

(ether); ν_max(KBr)/cm^Ϫ13058, 2216, 1592, 1569, 1515, 1482,

1437, 1406, 1387, 1344, 1187, 1107, 1015, 877, 854, 824, 748,

(C_quat), 91.75 (C_quat), 111.32 (C_quat), 118.54 (C_quat), 123.02

(C_quat), 125.95 (ϩ, CH), 126.52 (C_quat, J_C᎐P91.6 Hz), 128.05

(C_quat), 129.00 (ϩ, CH, J_C–P12.2 Hz), 131.73 (ϩ, CH), 132.00

(ϩ, CH), 132.32 (ϩ, CH, J_C–P2.4 Hz), 133.13 (ϩ, CH, J_C–P9.7

1

Hz), 133.40 (ϩ, CH), 151.45 (C_quat, J 16.0 Hz), 176.70 (C_quat

,

C᎐O); MS (FAB, 3-nitrobenzyl alcohol) m/z 512 (18%). HRMS

᎐

found: 512.1240; calcd. for C₃₃H₂₃ONPS: 512.1238.

1-[p-(2-Thienyl)benzoyl]-2-(p-tolyl)ethene (11c)—general

procedure C

A mixture of p-tolualdehyde (10a) (45 mg, 0.36 mmol), 4j (102

mg, 0.22 mmol) and benzoic acid (5 mg, 4.0 ×10^Ϫ2mmol) in

benzene (1.5 mL) were held at reﬂux for 11 h. After the reaction

solution had cooled, the solvent was evaporated in vacuo and

the residue was subjected to column chromatography on silica

gel (eluant: hexane–CHCl₃1 : 1) to give 11c (66 mg, 98%) as

a colorless solid; R_f0.25 (hexane–CHCl₃); mp 186 crystal to

crystal transition 197 (hexane–ether) (Found: C, 77.63; H, 5.14.

C₂₀H₁₆OSؒ0.25 H₂O requires C, 77.76; H, 5.38%); ν_max(KBr)/

cm^Ϫ13042, 3014, 2914, 1655, 1606, 1334, 1229, 1184, 1034, 983,

2

718, 692; δ_H(270 MHz, CDCl₃) 4.46 (1H, d, J_H–P23.8 Hz),

7.45–7.76 (19H, m), 7.98 (2H, d, ³J 8.6 Hz), 8.21 (2H, d, ³J 8.6

Hz); δ_CNMR (67.8 MHz, CDCl₃, DEPT 90, DEPT 135) 51.83

(CH, ¹J_C᎐P110.9 Hz), 88.30 (C_quat), 95.17 (C_quat), 122.66 (C_quat),

᎐

123.59 (CH), 126.69 (C_quat, ¹J_C–P91.3 Hz), 127.04 (CH), 128.91

(CH, J_C–P12.2 Hz), 130.35 (C_quat), 131.36 (CH), 132.20 (CH),

132.78 (CH), 133.10 (CH, J_C–P9.7 Hz), 141.97 (C_quat, J_C–P15.8

Hz), 146.86 (C_quat), 183.43 (C_quat, C᎐O, ²J_C–P2.4 Hz); MS (FAB,

᎐

2106

J. Chem. Soc., Perkin Trans. 1, 2002, 2090–2110

View Article Online

810, 692 cm; δ_H(270 MHz, CDCl₃) 2.40 (3H, s, CH₃), 7.13 (1H,

MS (70 eV) m/z 359 (64%), 211 (22), 153 (78). HRMS found:

359.1157; calcd. for C₂₂H₁₇O₄N: 359.1158.

3

m), 7.23 (2H, d, J 8.2 Hz), 7.37 (1H, m), 7.50 (2H, d, J 15.5

Hz), 7.56 (2H, d, ³J 8.2 Hz), 7.73 (2H, d, ³J 8.3 Hz), 7.83 (1H, d,

3

³J 15.5 Hz), 8.04 (2H, d, J 8.3 Hz); δ_C(67.8 MHz, CDCl₃,

1-[o-( p-Fluorophenyl)benzoyl]-2-(p-tolyl)ethene (11g)

DEPT 90, DEPT 135) 21.56 (CH₃), 120.86 (CH), 124.56 (CH),

125.70 (CH, 2C), 126.39 (CH), 128.37 (CH), 128.51 (CH,

2C), 129.30 (CH, 2C), 132.20 (CH, 2C), 132.20 (C_quat), 136.98

(C_quat), 138.47 (C_quat), 141.13 (C_quat), 143.11 (C_quat), 144.88

A mixture of p-tolualdehyde (10a) (70 mg, 0.55 mmol), 6c

(164 mg, 0.34 mmol) and benzoic acid (30 mg, 0.25 mmol)

in benzene (4 mL) was held at reﬂux for 24 h. The reaction

mixture was concentrated in vacuo and directly subjected to

column chromatography on silica gel (eluant: chloroform–

hexane 1 : 2.5–1 : 2) to give 11g (48 mg, 45%); ν_max(neat)/cm^Ϫ1

3058, 3026, 2922, 1665, 1601, 1513, 1326, 1223, 761; δ_H(270

MHz, CDCl₃) 2.33 (3H, s, CH₃), 6.55 (1H, d, ³J 15.8 Hz), 7.04

(2H, m), 7.12 (2H, d, ³J 8.5 Hz), 7.17 (2H, d, ³J 8.5 Hz), 7.25–

(CH), 189.57 (C_quat, C᎐O); MS (70 eV) m/z 304 (M^ϩ, 91%), 289

᎐

(M^ϩϪ CH₃), 187 (25), 115 (100). HRMS found: 304.0917;

calcd. for C₂₀H₁₆OS: 304.0922.

1-[p-(Methoxyphenyl)benzoyl]-2-(p-tolyl)ethene (11b)

3

A mixture of p-tolualdehyde (10a) (45 mg, 0.36 mmol), 4a

(107 mg, 0.22 mmol), benzoic acid (26 mg, 0.21 mmol) in

benzene (2 mL) was held at reﬂux for 24 h. The reaction was

worked up as described in procedure C to give 11b (71 mg, 98%)

as a mixture of (E)- and (Z)-isomers (E/Z). The (E)-isomer

could be crystallized from ether to give pale yellow crystals, mp

211–213 ЊC (ether); ν_max(KBr)/cm^Ϫ13012, 2916, 2836, 1659,

1604, 1290, 1258, 1200, 1037, 827, 810; δ_H(270 MHz, CDCl₃,

¹H–¹H-COSY) 2.41 (3H, s, CH₃), 3.88 (3H, s, OCH₃), 7.01 (2H,

d, ³J 8.2 Hz), 7.24 (2H, d, ³J 8.9 Hz), 7.53 (1H, d, ³J 15.8 Hz),

7.55–7.73 (4H, m), 7.69 (2H, d, ³J 7.9 Hz), 7.83 (1H, d, ³J 15.8

7.56 (6H, m), 7.35 (1H, d, J 15.8 Hz), δ_C(67.8 MHz, CDCl₃,

3

DEPT 90, DEPT 135) 21.49 (ϩ, CH₃), 115.51 (ϩ, CH, J_C–F

20.7 Hz), 125.78 (ϩ, CH), 127.49 (ϩ, CH), 128.22 (ϩ, CH),

128.35 (ϩ, CH, J_C–F17.0 Hz), 129.59 (ϩ, CH), 130.15 (ϩ, CH),

130.64 (ϩ, CH), 130.76 (ϩ, CH), 131.75 (C_quat), 136.52 (C_quat

,

J_C–F3.7 Hz), 139.75 (C_quat), 139.85 (C_quat), 141.11 (C_quat), 144.54

(ϩ, CH), 162.50 (C_quat, J_C–F(Ϫ)247 Hz), 196.56 (C_quat, C᎐O);

᎐

MS (FAB, 3-nitrobenzyl alcohol) m/z 317 (MH^ϩ, 100%), 199

(F-Ph-Ph-CO^ϩ, 41); EI (70 eV) m/z 316 (M^ϩ, 100%), 301 (M^ϩϪ

CH₃, 76), 222 (M^ϩϪ [F-Ph], 33), 207 (M^ϩϪ 15, 44), 199 (17).

HRMS found: 316.1261; calcd. for C₂₂H₁₇OF: 316.1263.

3

Hz), 8.09 (2H, d, J 7.9 Hz); δ_C(67.8 MHz, CDCl₃, DEPT 90,

DEPT 135) 21.56 (CH₃), 55.38 (OCH₃), 114.39 (CH), 121.00

(CH), 126.66 (CH), 128.44 (CH), 129.13 (CH), 129.70 (CH),

132.22 (C_quat), 132.36 (C_quat), 136.44 (C_quat), 141.04 (C_quat),

144.69 (CH), 145.03 (C_quat), 159.87 (C_quat), 189.95 (C_quat); MS

(70 eV) m/z 328 (M^ϩ, 100%); 313 (M^ϩϪ CH₃, 33), 148 (42);

HRMS found: 328.1463; calcd. for C₂₃H₂₀O₂: 328.1463.

17-Bromo-3-methoxy-16-{[m-(4-vinylphenyl)benzoyl]ethenyl}-

estra-1,3,5(10),16-tetraene (13a)

A mixture of 12 (41 mg, 0.11 mmol), 7e (58 mg, 0.12 mmol) and

benzoic acid (15 mg, 0.12 mmol) was held at reﬂux for 20 h. The

cooled solution was concentrated in vacuo and the residue was

subjected to column chromatography on silca gel (hexane–ether

3 : 1) to give 13a (48 mg, 75%) as colorless plates, mp 201–203

ЊC (hexane–ether 3 : 1); ν_max(KBr)/cm^Ϫ12926, 2854, 1657, 1580,

1499, 1309, 1255, 1192, 1021, 906, 842, 801, 729; δ_H(270 MHz,

CDCl₃) 0.94 (3H, s, CH₃), 1.45–2.38 (10H, m), 2.60 (1H, dd,

²J 13.8, ³J 6.6 Hz), 2.91 (2H, m), 3.78 (3H, s, OCH₃), 5.30 (1H,

1-[p-( p-Fluorophenyl)benzoyl]-2-(p-tolyl)ethene (11d)

A mixture of p-tolualdehyde (10a) (51 mg, 0.41 mmol), 4d

(102 mg, 0.22 mmol) and benzoic acid (6 mg, 4.85 × 10^Ϫ2mmol)

were held at reﬂux for 12 h. The reaction was worked up as

described in procedure C. Column chromatography on silica gel

(CHCl₃–hexane 1 : 2) yielded 11d (61 mg, 90%) as oﬀ-white

needles; R_f0.20 (CHCl₃–hexane 1 : 2); mp 209–210 ЊC (ether)

(Found: C, 82.35; H, 5.45. C₂₂H₁₇OFؒ0.25H₂O requires C,

82.35; H, 5.49%); ν_max(KBr)/cm^Ϫ13062, 2920, 1654, 1597, 1242,

1196, 812; δ_H(270 MHz, CDCl₃) 2.40 (3H, s, CH₃), 7.13–7.25

(4H, m), 7.49–7.64 (5H, m), 7.68 (2H, d, ³J 8.2 Hz), 7.83 (1H, d,

3

d, J 11.2 Hz), 5.81 (1H, d, J 17.4 Hz), 6.66 (1H, br s), 6.72

(1H, m), 6.77 (1H, dd, ³J 11.2, ³J 17.4 Hz), 6.97 (1H, d, J 15.4

Hz), 7.20 (1H, d, ³J 8.7 Hz), 7.52 (2H, d, ³J 8.6 Hz), 7.57 (1H, d,

³J 7.6 Hz), 7.61 (2H, d, ³J 8.6 Hz), 7.75 (1H, d, ³J 15.4 Hz), 7.76

3

(1H, m), 7.91 (1H, d, J 7.6 Hz), 8.16 (1H, s); δ_C(67.8 MHz,

CDCl₃, DEPT 135, DEPT 90) 15.60 (ϩ, CH₃), 26.18 (Ϫ), 27.31

(Ϫ), 29.58 (Ϫ), 31.27 (Ϫ), 34.71 (Ϫ), 37.56 (ϩ, CH), 42.22 (ϩ,

CH), 51.19 (C_quat), 53.39 (ϩ, CH), 55.22 (ϩ, OCH₃), 111.53 (ϩ,

CH), 113.94 (ϩ, CH), 114.32 (Ϫ), 124.33 (ϩ, CH), 126.00

(ϩ, CH), 126.79 (ϩ, CH, 2C), 126.97 (ϩ, CH), 127.36 (ϩ, CH,

2C), 129.05 (ϩ, CH), 131.16 (ϩ, CH), 132.20 (C_quat), 136.28 (ϩ,

CH), 136.58 (C_quat), 137.14 (C_quat), 137.66 (C_quat), 138.77 (C_quat),

138.94 (ϩ, CH), 139.64 (C_quat), 141.29 (C_quat), 146.20 (C_quat),

3

³J 15.8 Hz), 8.09 (2H, d, J 8.2 Hz); δ_C(67.8 MHz, CDCl₃,

3

DEPT 90, DEPT 135) 21.55 (ϩ, CH₃), 115.90 (ϩ, CH, J_C–F

21.8 Hz), 120.99 (ϩ, CH), 127.10 (ϩ, CH), 128.52 (ϩ, CH),

128.94 (ϩ, CH, J_C–F8.5 Hz), 129.15 (ϩ, CH), 129.74 (ϩ, CH),

132.18 (C_quat), 136.13 (C_quat, J_C–F3.7 Hz), 137.09 (C_quat), 141.15

(C_quat), 144.37 (C_quat), 144.96 (ϩ, CH), 162.94 (C_quat, J_C–F

(Ϫ)240 Hz), 189.95 (C_quat, C᎐O); MS (70 eV) m/z 316 (M^ϩ,

157.64 (C_quat), 190.85 (C_quat, C᎐O); MS (FAB, 3-nitrobenzyl

᎐

100%), 301 (M^ϩϪ CH₃, 85). HRMS found: 316.1264; calcd. for

alcohol) m/z 581 ([⁸¹Br]MH^ϩ, 8%), 579 ([⁷⁹Br]MH^ϩ, 9). HRMS

C₂₂H₁₇OF: 316.1263.

found: 579.1899; calcd. for C₃₆H₃₆O₂⁷⁹Br: 579.1899.

1-[p-( p-Methoxyphenyl)benzoyl]-2-(p-nitrophenyl)ethene (11e)

17-Bromo-3-methoxy-16-[2-( p-{4-[(E )-2-(methoxycarbonyl)-

ethenyl]phenyl}benzoyl)ethenyl]estra-1,3,5(10),16-tetraene (13b)

A mixture of p-nitrobenzaldehyde (10b) (61 mg, 0.40 mmol), 4a

(106 mg, 0.22 mmol) and benzoic acid (12 mg, 9.7 × 10^Ϫ2mmol)

in benzene (2.0 mL) were held at reﬂux for 12 h. The reaction

was worked up as described in procedure C. Column chroma-

tography on silica gel (CHCl₃–hexane 2 : 1) yielded 11e (77 mg,

97%) as a mixture of (E)- and (Z)-isomers. The (E)-isomer

could be crystallized from ether to give 11e as yellow crystals;

mp 97 ЊC (ether); ν_max(KBr)/cm^Ϫ13080, 2962, 2836, 1656, 1597,

1518, 1494, 1345, 1318, 1292, 1257, 1198, 1029, 818; δ_H(270

A mixture of 12 (41 mg, 0.11 mmol), 8c (52 mg, 0.11 mmol),

and benzoic acid (15 mg, 0.12 mmol) in benzene (1.5 mL) was

reacted at 80 ЊC for 20 h. Thereafter the solution was cooled

and concentrated in vacuo. The residue was subjected to column

chromatography on silica gel (ether–hexane 1 : 1) to give 13b

(52 mg, 85%) as a colorless powder; mp 177–178 ЊC (ether–

hexane 1 : 1); ν_max(KBr)/cm^Ϫ12926, 1717, 1656, 1604, 1585,

1499, 1308, 1280, 1211, 1171, 829; δ_H(270 MHz, CDCl₃) 0.94

1

2

3

MHz, CDCl₃, H–¹H-COSY) 3.88 (3H, s, OCH₃), 7.02 (2H, d,

(3H, s, CH₃), 1.40–2.43 (11H, m), 2.60 (1H, dd, J 14.8, J 6.6

Hz), 2.93 (2H, m), 3.79 (3H, s, OCH₃), 3.83 (3H, s, OCH₃), 6.65

(1H, d, ⁴J 3.0 Hz), 6.73 (1H, dd, ³J 7.9, ⁴J 3.0 Hz), 6.93 (1H, d,

³J 16.2 Hz), 7.23 (1H, d, ³J 7.9 Hz), 7.63 (2H, d, ³J 8.2 Hz), 7.73

³J 8.9 Hz), 7.61 (2H, d, ³J 8.9 Hz), 7.66–7.88 (4H, m), 8.10 (2H,

3

d, J 8.6 Hz), 8.29 (2H, d, J 8.9 Hz); δ_C(67.8 MHz, CDCl₃)

55.40 (OCH₃), 114.47, 124.23, 125.70, 126.83, 128.41, 128.91,

129.27, 132.06, 135.60, 141.15, 141.24, 145.73, 160.07, 188.91;

3

(2H, d, J 16.2 Hz), 7.97 (2H, d, J 8.2 Hz); δ_C(67.8 MHz,

J. Chem. Soc., Perkin Trans. 1, 2002, 2090–2110 2107

View Article Online

CDCl₃, DEPT 90, DEPT 135) 15.60 (ϩ, CH₃), 26.18 (Ϫ), 27.31

(Ϫ), 29.58 (Ϫ), 31.25 (Ϫ), 34.72 (Ϫ), 37.57 (ϩ, CH), 44.24 (ϩ,

CH), 51.25 (C_quat), 51.91 (ϩ, OCH₃), 53.40 (ϩ, CH), 55.24 (ϩ,

OCH₃), 111.52 (ϩ, CH), 113.96 (ϩ, CH), 120.18 (ϩ, CH),

123.93 (ϩ, CH), 126.02 (ϩ, CH), 128.17 (ϩ, CH, 2C), 129.04

(ϩ, CH, 2C), 132.18 (C_quat), 136.55 (C_quat), 137.64 (C_quat),

138.34 (C_quat), 139.15 (ϩ, CH), 139.30 (C_quat), 143.47 (ϩ, CH),

1-[p-(2-Thienyl)benzoyl]-2-(p-tolyl)ethene (11c)—general

procedure E

A mixture of p-tolualdehyde (80 mg, 0.66 mmol), 4j (166 mg,

0.33 mmol), 2-thienylboronic acid (85 mg, 0.66 mmol) and

Pd(PPh₃)₄(24 mg, 2.0 × 10^Ϫ2mmol) in DME (2.5 mL) and 2 M

aq. Na₂CO₃(1.3 mL) was held at 85 ЊC for 24 h. After the

reaction solution had cooled, water (5 mL) was added and

the mixture was extracted with chloroform (3 × 10 mL). The

organic phase was dried over anhydrous MgSO₄. Thereafter, the

solvent was evaporated in vacuo and the residue was subjected

to column chromatography on silica gel (eluant: hexane–CHCl₃

1 : 1) to give 11c (79 mg, 79%) after recrystallization from

hexane–ether (3 : 1).

146.61 (C_quat), 157.66 (C_quat), 167.01 (C_quat, C᎐O), 189.95 (C

,

᎐

quat

C᎐O); MS (FAB, 3-nitrobenzyl alcohol) m/z 563 ([⁸¹Br]MH^ϩ,

᎐

11%), 561 ([⁷⁹Br]MH^ϩ, 12). HRMS found: 561.1637; calcd. for

C₃₂H₃₄O₄⁷⁹Br: 561.1640.

17-Bromo-3-methoxy-16-(2-{[p-(4-vinylphenyl)benzoyl]}-

ethenyl)estra-1,3,5(10),16-tetraene (13c)

A mixture of 12 (30 mg, 0.08 mmol), phosphorane 4i (37 mg,

0.08 mmol), benzoic acid (10 mg, 0.08 mmol) in benzene (2 mL)

were heated at 80 ЊC for 20 h. Thereafter the cooled solution

was concentrated in vacuo and the residue was subjected to

column chromatography on silica gel (ether–hexane 1 : 4) to

give 13c (28 mg, 60%) as a colorless powder; mp 190–191 ЊC

(ether–hexane 1 : 4); ν_max(KBr)/cm^Ϫ12924, 2852, 1657,

1605, 1589, 1498, 1304, 1278, 1038, 824; δ_H(270 MHz, CDCl₃,

¹H–¹H-COSY) 0.95 (3H, s, CH₃), 1.55–2.61 (11H, m), 2.93 (2H,

1-[p-( p-Fluorophenyl)benzoyl]-2-(p-tolyl)ethene (11d)

A mixture of p-tolualdehyde (10a) (80 mg, 0.66 mmol), 3a

(166 mg, 0.33 mmol), p-ﬂuorophenylboronic acid (93 mg,

0.66 mmol) and Pd(PPh₃)₄(34 mg, 2.8 × 10^Ϫ2mmol) in DME

(2.5 mL) and 2 M aq. Na₂CO₃(1.3 mL) was reacted according

to general procedure E (reaction time: 24 h). Column chroma-

tography on silica gel (hexane–CHCl₃3 : 2) and recrystalliza-

tion in hexane furnished 11d (73 mg, 70%).

3

m), 3.79 (3H, s, OCH₃), 5.32 (1H, d, J 10.9 Hz), 5.83 (1H, d,

3

³J 16.8 Hz), 6.66 (1H, br s), 6.73 (1H, dd, J 16.8, J 10.9 Hz),

7.00 (1H, d, ³J 15.2 Hz), 7.22–7.32 (2H, m), 7.51 (2H, d, ³J 8.6

Hz), 7.62 (2H, d, ³J 8.6 Hz), 7.68 (2H, d, ³J 8.6 Hz), 7.75 (1H, d,

³J 15.2 Hz), 8.04 (2H, d, ³J 8.6 Hz); δ_C(67.8 MHz, CDCl₃) 15.62

(ϩ, CH₃), 26.20 (Ϫ), 27.33 (Ϫ), 29.60 (Ϫ), 31.28 (Ϫ), 34.73 (Ϫ),

37.57 (ϩ, CH), 44.26 (ϩ, CH), 51.19 (C_quat), 53.42 (ϩ, CH),

55.24 (ϩ, OCH₃), 111.53 (ϩ, CH), 113.96 (ϩ, CH), 114.57 (Ϫ),

124.22 (ϩ, CH), 126.02 (ϩ, CH), 126.83 (ϩ, CH, 2C), 127.02

(ϩ, CH, 2C), 127.40 (ϩ, CH, 2C), 129.13 (ϩ, CH, 2C), 132.24

(C_quat), 136.22 (ϩ, CH), 136.60 (C_quat), 136.91 (C_quat), 137.57

(C_quat), 137.68 (C_quat), 138.63 (ϩ, CH), 139.24 (C_quat), 144.94

1-[p-(2-Thienyl)benzoyl]-2-(o-nitrophenyl)ethene (11h)

A mixture of p-tolualdehyde (10a) (100 mg, 0.66 mmol), 3a

(166 mg, 0.33 mmol), 2-thienylboronic acid (85 mg, 0.66 mmol)

and Pd(PPh₃)₄(24 mg, 2.0 × 10^Ϫ2mmol) in DME (2.5 mL) and

2 M aq. Na₂CO₃(1.3 mL) was reacted according to general

procedure E (reaction time: 24 h). Column chromatography on

silica gel (hexane–CHCl₃1 : 1) and recrystallization in hexane

furnished 11h (88 mg, 75%) as a yellow solid; mp 155–156 ЊC

(hexane) (Found: C, 67.71; H, 3.96; N, 4.21. C₁₉H₁₃NO₃S

requires C, 68.05; H, 3.91; N, 4.18%); ν_max(KBr)/cm^Ϫ12924,

2852, 1652, 1604, 1520, 1339, 1292, 1223, 1187, 856, 815;

δ_H(270 MHz, CDCl₃) 7.13 (1H, dd, ³J 5.1, ³J 3.9 Hz), 7.33 (1H,

d, ³J 15.8 Hz), 7.38 (1H, m), 7.46 (1H, d, ³J 3.9 Hz), 7.58 (1H,

m), 7.75 (2H, d, ³J 7.9 Hz), 7.75 (2H, m), 8.05 (2H, d, ³J 7.9 Hz),

(C_quat), 146.02 (C_quat), 157.64 (C_quat), 190.20 (C_quat, C᎐O); MS

᎐

(FAB, 3-nitrobenzyl alcohol) m/z 581 ([⁸¹Br]MH^ϩ, 0.6%), 579

([⁷⁹Br]MH^ϩ, 0.6). HRMS found: 579.1896; calcd. for C₃₆-

H₃₆O₂⁷⁹Br: 579.1899.

3

8.07 (1H, m), 8.16 (1H, d, J 15.8 Hz); δ_CNMR (67.8 MHz,

7ꢀ-[12-(Phenylethynylbenzoyl)dodec-11-enyl]-17,17-(2,2-di-

methylpropane-1,3-diyldioxy)-3-O-methylestra-1,3,5(10)-triene

(15)

CDCl₃, DEPT 90, DEPT 135) 124.76 (ϩ, CH), 125.03 (ϩ, CH),

125.82 (ϩ, CH, 2C), 126.61 (ϩ, CH), 127.30 (ϩ, CH), 128.41

(ϩ, CH), 129.29 (ϩ, CH), 129.67 (ϩ, CH, 2C), 130.33 (ϩ, CH),

131.40 (C_quat), 133.55 (ϩ, CH), 135.80 (C_quat), 139.10 (C_quat),

To 14 (35 mg, 0.06 mmol) in benzene (1.5 mL) were added

benzoic acid (20 mg, 0.16 mmol) and the phosphorane 9a

(91 mg, 0.18 mmol). The resulting reaction mixture was held at

reﬂux for 15 h. Then, the solution was concentrated in vacuo

and subjected to column chromatography on silica gel

(toluene–ethyl acetate 15 : 1) to give 15 (24 mg, 51%) as a pale

yellow oil; R_f0.68; ν_max(KBr)/cm^Ϫ13014, 2926, 2854, 1674,

1606, 1493, 1464, 1288, 1215, 1105, 1035, 756; δ_H(270 MHz,

CDCl₃) 0.74 (3H, s, CH₃), 0.83 (3H, s, CH₃), 1,17 (3H, s, CH₃),

1.23–1.74 (22H, m), 1.93–2.12 (3H, m), 2.25–2.48 (6H, m),

2.68–2.76 (1H, m), 3.37–3.50 (3H, m), 3.67 (1H, d, J 11.2 Hz),

3.84 (3H, s, OCH₃), 6.88 (1H, d, J 15.5 Hz), 7.04–7.38 (6H, m),

140.07 (ϩ, CH), 142.90 (C_quat), 145.35 (C_quat), 189.40 (C_quat, C᎐

᎐

O); MS (70 eV) m/z 335 (M^ϩ, 14%), 303 (9), 289 (35), 187 (95),

115 (100). HRMS found: 335.0614; calcd. for C₁₉H₁₃O₃NS:

335.0616.

1-[p-(2-Thienyl)benzoyl]-2-cyclohexylethene (11i)

A mixture of cyclohexanecarbaldehyde (10d) (74 mg, 0.66

mmol), 3a (166 mg, 0.33 mmol), 2-thienylboronic acid (16a)

(85 mg, 0.66 mmol) and Pd(PPh₃)₄(24 mg, 2.0 × 10^Ϫ2mmol)

in DME (2.5 mL) and 2 M aq. Na₂CO₃(1.3 mL) was reacted

according to general procedure E (reaction time: 17 h). Column

chromatography on silica gel (hexane–CHCl₃1 : 1) and

recrystallization in hexane furnished 11i (78 mg, 80%) as a pale

yellow solid; mp 82–83 ЊC (hexane) (Found: C, 76.82; H, 6.88.

C₁₉H₂₀OS requires C, 76.99; H, 6.80%); ν_max(KBr)/cm^Ϫ12916,

2846, 1657, 1609, 1596, 1422, 815, 685; δ_H(270 MHz, CDCl₃)

1.16–1.43 (4H, m), 1.68–1.87 (6H, m), 2.27 (1H, m), 6.84 (1H,

3

7.52–7.57 (3H, m), 7.62 (2H, d, J 8.2 Hz), 7.92 (2H, d, J 8.2

Hz); δ_C(67.9 MHz, CDCl₃, DEPT 90, DEPT 135) 17.80 (ϩ,

CH₃), 22.02 (ϩ, CH₃), 22.27 (Ϫ), 22.52 (ϩ, CH₃), 23.83 (Ϫ),

26.55 (Ϫ), 26.93 (Ϫ), 27.42 (Ϫ), 28.17 (Ϫ), 29.25 (Ϫ), 29.35 (Ϫ),

29.37 (Ϫ), 29.48 (Ϫ), 29.55 (Ϫ), 29.72 (Ϫ), 30.38 (Ϫ), 32.92 (Ϫ),

37.32 (ϩ, CH), 42.81 (ϩ, CH), 42.92 (ϩ, CH), 47.36 (C_quat),

48.86 (ϩ, CH), 55.45 (ϩ, OCH₃), 70.75 (Ϫ), 72.61 (Ϫ), 88.75

(C_quat), 92.45 (C_quat), 108.38 (C_quat), 110.00 (ϩ, CH), 121.38 (ϩ,

CH), 122.73 (C_quat), 125.55 (ϩ, CH), 127.23 (ϩ, CH), 127.66

(C_quat), 128.43 (ϩ, CH), 128.51 (ϩ, CH), 128.75 (ϩ, CH),

131.65 (ϩ, CH), 131.74 (ϩ, CH), 132.31 (C_quat), 137.20 (C_quat),

139.03 (C_quat), 150.52 (ϩ, CH), 158.07 (C_quat), 189.97 (C_quat),

201.42 (C_quat); MS (FAB, 3-nitrobenzyl alcohol) m/z (754, M^ϩ);

HRMS (FAB) found 755.4672 (MH^ϩ); calcd. for C₅₁H₆₃O₅:

755.4676.

3

4

3

dd, J 15.5, J 1.3 Hz), 7.03 (1H, dd, J 15.5, J 6.6 Hz), 7.12

(1H, dd, ³J 3.9, ³J 5.0 Hz), 7.42 (1H, dd, ³J 3.9, ⁴J 1.0 Hz), 7.36

(1H, dd, ³J 5.0, ⁴J 1.0 Hz), 7.70 (2H, d, ³J 8.6 Hz), 7.94 (2H, d,

³J 8.6 Hz); δ_C(67.8 MHz, CDCl₃, DEPT 90, DEPT 135) 25.77

(Ϫ), 25.98 (Ϫ), 31.90 (Ϫ), 41.09 (ϩ, CH), 123.20 (ϩ, CH),

124.49 (ϩ, CH), 125.66 (ϩ, CH, 2C), 126.32 (ϩ, CH), 128.35

(ϩ, CH), 129.36 (ϩ, CH, 2C), 136.80 (C_quat), 138.36 (C_quat),

143.14 (C_quat), 154.84 (ϩ, CH), 190.35 (C_quat, C᎐O); MS (70 eV)

᎐

2108

J. Chem. Soc., Perkin Trans. 1, 2002, 2090–2110

View Article Online

m/z 296 (M^ϩ, 58%), 187 (100), 115 (24). HRMS found:

ment on F ²with all non-hydrogen atoms anisotropic and

296.1236; calcd. for C₁₉H₂₀OS: 296.1235.

hydrogens in calculated positions with U_iso= 1.3 U_(bonded

atoms)

2

was performed. The weighting scheme is w = 1/[σ²(F_o) ϩ

(0.0976 P)²ϩ 0.0000 P], where P = (F_o²ϩ 2 Fc²)/3. Final R and

R_wvalues for 3186 reﬂections with I > 3.00 σ(I) are 0.0694,

0.1643 (reﬁned on F ²). All calculations were performed on

a Gateway GP7-7000 using SIR92,⁴³Texsan,⁴⁴Oscail⁴⁵and

SHELXL-97–2.⁴⁶

Approach to the preparation of elongated phosphoranes and their

coupling reactions on a solid support

Under argon a mixture of 2-bromo-5-acetylthiophene (3b)

(1.14 g, 4.0 mmol) and TPPPS resin‡ (0.5 g, 0.8 mmol) in DME

(4 mL) was stirred at 60 ЊC for 6 h. Thereafter, the resin was

ﬁltered and diligently washed with THF and CH₂Cl₂and dried

in vacuo at rt.

Acknowledgements

Then under an inert atmosphere, the resin was added to dis-

tilled water (3 mL) and aq. 7w% Na₂CO₃(3 mL) was added

and the mixture was stirred for 3 h. The resin was washed

thoroughly with warm water (50 ЊC), THF (100 mL) and

CH₂Cl₂(100 mL) and subsequently dried in vacuo at rt.

Under an inert atmosphere, the resin was suspended in DME

(4 mL) at rt. Then, 2-ﬂuoroboronic acid (420 mg, 3 mmol), 2 M

aq. Na₂CO₃(3 mL) and Pd(PPh₃)₄(45 mg, 4 × 10^Ϫ5mol) were

added and the resulting mixture was stirred at 75 ЊC for 8 h.

Thereafter, the resin was isolated by ﬁltration and was washed

with distilled water (100 mL), THF (100 mL) and CH₂Cl₂

(100 mL) and dried in vacuo at rt.

The testing of compounds 4a, 4e, 4h, 4j, 5b, 5c, 5m, and 7d was

performed by the Developmental Therapeutics Program,

DCTD, NCI in Bethesda, Maryland, USA. The elemental

analyses were carried out at the Center of Analysis, Kyushu

University, Hakozaki Campus, Fukuoka.

References

1 For a review, see: H. Bestmann and O. Vostrowsky, Top. Curr.

Chem., 1983, 109, 85.

2 W. Tochtermann, Liebigs Ann./Recl., 1997, I.

3 (a) G. Wittig and M. Rieger, Justus Liebigs Ann. Chem., 1949, 562,

187; (b) G. Wittig and G. Geissler, Justus Liebigs Ann. Chem., 1953,

580, 44; (c) G. Wittig and U. Schöllkopf, Chem. Ber., 1954, 87, 1318.

4 O. I. Kolodiazhnyi, Phosphorus Ylides—Chemistry and Application

in Organic Synthesis, Wiley-VCH, Weinheim, 1999.

5 F. Ramirez and S. Dershowitz, J. Org. Chem., 1957, 22, 41.

6 S. Trippett and D. M. Walker, J. Chem. Soc., 1959, 3874.

7 They do react with cyclopropanone and cyclopropanone

hemiacetals: A. Brandi and A. Goti, Chem. Rev., 1998, 98, 589 and

refs. cited therein. See also refs. 30 and 31.

8 For a preliminary communication, see: T. Thiemann, K. Umeno,

D. Ohira, E. Inohae, T. Sawada and S. Mataka, New J. Chem., 1999,

23, 1067.

9 Alternative methods for the synthesis of alkyl-/arylcarbonyl-

methylidenetriphenylphosphorane are known which involve either

the acylation of methylenetriphenylphosphorane with an acyl

halide¹⁰or an activated ester¹¹or an acylation of methoxy-

The resin was suspended in benzene (5 mL) and steroidal

aldehyde (1.2 mmol) and benzoic acid (10 mg, 8 × 10^Ϫ5mol)

were added. The resulting mixture was stirred at 80 ЊC under

argon for 20 h. The resin was ﬁltered oﬀ and washed with

THF (50 mL) and CH₂Cl₂(50 mL). The combined ﬁltrate

was concentrated in vacuo and the residue was subjected to

column chromatography on silica gel (toluene–ether 10 : 1)

to give 17-bromo-3-methoxy-16-{(E)-2-[p-(o-ﬂuorophenyl)-

benzoyl]ethenyl}estra-1,3,5(10),16-tetraene (13d) (132 mg,

29%) as a pale yellow solid; R_f0.72; mp 185–186 ЊC; ν_max(KBr)/

cm^Ϫ12924, 1736, 1658, 1608, 1587, 1500, 1280, 1255, 1034, 820,

753; δ_H(270 MHz, CDCl₃) 0.94 (3H, s, CH₃), 1.43–2.45 (10H,

m), 2.62 (1H, dd, ²J 13.8, ³J 6.6 Hz), 2.93 (2H, m), 3.79 (3H, s,

OCH₃), 6.66 (1H, d, ⁴J 2.9 Hz), 6.73 (1H, dd, ³J 8.5, ⁴J 2.9 Hz),

7.00 (1H, d, ³J 15.5 Hz), 7.15–7.28 (3H, m), 7.36 (1H, m), 7.48

carbonylmethylidenetriphenylphosphorane

with

subsequent

removal of the methoxycarbonyl group.¹²All of these involve a

larger number of steps in the reaction sequence.

3

(1H, m), 7.70 (2H, m), 7.76 (1H, d, J 15.5 Hz), 8.05 (2H, d,

10 H. J. Bestmann and H. Schulz, Angew. Chem., 1961, 73, 27.

11 H. J. Bestmann and B. Arnason, Chem. Ber., 1962, 95, 1513.

12 G. Doleschall, Synthesis, 1981, 478.

13 T. Watanabe, N. Miyaura and A. Suzuki, Synlett, 1992, 207.

14 A. Suzuki, Cross Coupling Reactions of Organoboron Compounds

with Organic Halides, in Metal Catalyzed Cross-Coupling Reactions,

eds. F. Diederich and P. J. Stang, Wiley-VCH, Weinheim, 1998,

pp. 70–74.

15 S. M. Kelly, A. Germann, R. Buchecker and M. Schadt, Liq. Cryst.,

1994, 16, 67.

16 S. W. Wright, D. L. Hageman and L. D. McClure, J. Org. Chem.,

1994, 59, 6095.

17 Compound 4m was prepared from the p-formylphenylboronic acid

and trimethylene glycol in reﬂuxing benzene.

18 Compound 4p was prepared from 1-bromo-3,5-bis(trimethyl-

silylethynyl)benzene, 4n from bromo-1-benzothiophene and 4o from

dibenzothiophene by lithiation and reaction with trimethyl borate

with subsequent acidic work-up.

³J 8.2 Hz); δ_C(67.8 MHz, CDCl₃) 15.58, 26.17, 27.30, 29.58,

31.23, 34.68, 37.52, 44.21, 51.16, 53.35, 55.22, 111.50, 113.91,

116.30 (³J_C–F21.8 Hz), 124.08, 124.55, 126.00, 128.62, 129.20,

129.79, 129.92, 130.63, 132.18, 136.57, 137.18, 137.66, 138.72,

140.20, 146.13, 157.59, 159.75 (¹J_C–F(Ϫ)263 Hz), 190.22; MS

(70 eV) m/z 572 ([⁸¹Br]M^ϩ, 18%), 570 ([⁷⁹Br]M^ϩ, 16). HRMS

found: 570.1572; calcd. for C₃₄H₃₂O₂⁷⁹BrF: 570.1570.

X-Ray crystal structure determination of 4l§

Crystal data. C₃₆H₂₇OP, M = 506.55. Crystal system: mono-

clinic, unit cell dimensions: a = 15.4024(9), b = 8.0545(4), c =

21.492(1) Å, β = 96.1(8)Њ V = 2651(2) Å³, space group P21/c,

Z= 4, D_c= 1.269 g cm^Ϫ3, colorless, platelet, crystal size 0.40 ×

0.20 × 0.05 mm, µ(Mo-Kα) = 0.132 mm^Ϫ1

.

19 Typical examples are: 4Ј-acetyl-4-methoxybiphenyl, colorless solid,

mp 152 ЊC (lit. 153–154 ЊC^47a): ν_max(neat)/cm^Ϫ12956, 2840, 1674,

1399, 1361, 1294, 1032, 1011, 816; δ_H(270 MHz, CDCl₃) 2.63 (3H, s,

CH₃), 3.86 (3H, s, OCH₃), 7.00 (2H, d, ³J 8.6 Hz), 7.57 (2H, d, ³J 8.6

Hz), 7.64 (2H, d, ³J 8.6 Hz), 8.01 (2H, d, ³J 8.6 Hz); δ_C(67.8 MHz,

CDCl₃, DEPT 90, DEPT 135) 26.58 (ϩ, CH₃), 55.36 (ϩ, OCH₃),

114.41 (ϩ, CH, 2C), 126.59 (ϩ, CH, 2C), 128.36 (ϩ, CH, 2C),

128.93 (ϩ, CH, 2C), 132.25 (C_quat), 135.29 (C_quat), 145.37 (C_quat),

Data collection and processing. Rigaku RAXIS-RAPID,

Imaging Plate, graphite-monochromated Mo-Kα radiation;

6425 reﬂections were measured (1.33 ≤ θ ≤ 27.48Њ, 0 ≤ h ≤ 20,

0 ≤ k ≤ 10, Ϫ27 ≤ l ≤ 27). 6007 unique [max, min. transmission

factor = 0.9492, 0.9934], linear and approx. isotopic crystal

decay, ca. 0.0% corrected during procedure, measurement

temperature 183.2 K.

159.93 (Cquat), 197.70 (Cquat, C᎐O); MS (70 eV) m/z 226 (M^ϩ,

᎐

78%), 211 (M^ϩϪ CH₃, 100), 183 (10), 168 (14), 139 (19). HRMS:

found: 226.0995; calcd. for C₁₅H₁₄O₂: 226.0994; 4Ј-acetyl-4-

ﬂuorobiphenyl, colorless solid, mp 88 ЊC (lit. 90 ЊC^47b): ν_max(neat)/

cm^Ϫ12926, 1681, 1604, 1395, 906, 819, 731; δ_H(270 MHz, CDCl₃)

Structure analysis and reﬁnement. The structure was solved

by direct methods (SIR92).⁴³Full-matrix least-squares reﬁne-

3

2.64 (3H, s, COCH₃), 7.16 (2H, dd, J 8.2, J_H–F8.5 Hz), 7.59 (2H,

dd, ³J 8.2, ⁴J_H–F5.3 Hz), 7.64 (2H, d, ³J 8.2 Hz), 8.02 (2H, d, ³J 8.2

Hz); δ_C(67.8 MHz, CDCl₃, DEPT 90, DEPT 135) 26.63 (ϩ, CH₃),

115.91 (ϩ, CH, 2C, ²J_C–F20.8 Hz), 127.06 (ϩ, CH, 2C), 128.97 (ϩ,

‡ At the beginning of all the reaction sequences, the solid support was

‘pre-swelled’ in the solvent for 1 h before use.

§ CCDC reference number 182734. See http://ww w .rsc.org/suppdata/

p1/b2/b202745n/ for crystallographic ﬁles in .cif or other electronic

format.

4

CH, 4C), 135.87 (C_quat, J_C–F2.5 Hz), 136.01 (C_quat), 144.74 (C_quat),

163.00 (C_quat,

¹J_C–F247.8 Hz), 197.66 (C_quat, C᎐O); MS (70 eV)

᎐

J. Chem. Soc., Perkin Trans. 1, 2002, 2090–2110

2109

View Article Online

m/z 214 (M^ϩ, 48%), 199 (100), 170 (55). HRMS: found: 214.0793;

calcd. for C₁₄H₁₁OF: 214.0794; 5-acetylbithiophene, pale yellow

solid, mp 112 ЊC (lit. 113 ЊC;^47c108–111 ЊC^47d); ν_max(KBr)/cm^Ϫ13080,

2924, 1651, 1448, 1359, 1310, 1278, 1034, 932, 835, 802, 716, 691;

δ_H(270 MHz, CDCl₃) 2.55 (3H, s, CH₃), 7.06 (1H, dd, ³J 3.9, ³J 4.6

Hz), 7.17 (1H, d, J 3.9 Hz), 7.33 (2H, m), 7.59 (1H, d, J 3.9 Hz);

δ_C(67.8 MHz, CDCl₃, DEPT 90, DEPT 135) 26.53 (ϩ, CH₃), 124.13

(ϩ, CH), 125.62 (ϩ, CH), 126.49 (ϩ, CH), 128.23 (ϩ, CH), 131.90

31 For other one-pot reactions utilizing stabilized phosphoranes, see:

T. Thiemann, D. Ohira, Y. Li, T. Sawada, S. Mataka, K. Rauch,

M. Noltemeyer and A. de Meijere, J. Chem. Soc., Perkin Trans. 1,

2000, 2968.

32 (a) T. Thiemann, C. Thiemann, S. Sasaki, V. Vill, S. Mataka and

M. Tashiro, J. Chem. Res. (S), 1997, 248; (b) T. Thiemann,

C. Thiemann, S. Sasaki, V. Vill, S. Mataka and M. Tashiro, J. Chem.

Res. (M), 1997, 1736.

3

(C_quat), 132.10 (C_quat), 133.28 (ϩ, CH), 142.44 (C_quat), 198.15 (C_quat

᎐

,

33 M. C. Melo e Silva, L. Patrício, L. Gano, M. L. Sá e Melo,

E. Inohae, S. Mataka and T. Thiemann, Appl. Radiat. Isot., 2001, 54,

227.

34 E. Inohae, T. Thiemann, S. Mataka, M. C. Melo e Silva and

L. Patricio, Rep. Inst. Adv. Mater. Stud. Kyushu Univ., 1999, 13(1),

31.

35 (a) T. Thiemann, K. Umeno, E. Inohae, M. Imai, Y. Shima and

S. Mataka, J. Chem. Res., 2002(S), 1–3; (b) T. Thiemann, K. Umeno,

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C᎐O); MS (70 eV) m/z 208 (M^ϩ, 76%), 193 (M^ϩϪ CH₃, 100).

HRMS: found: 208.0017; calcd. for C₁₀H₈OS₂: 208.0017; p-acetyl-

phenylbenzothiophene, ν_max(KBr)/cm^Ϫ12922, 2850, 1674, 1261, 819;

δ_H(270 MHz, CDCl₃) 2.57 (3H, s, CH₃), 7.28 (2H, m), 7.61 (1H, s),

7.76 (2H, d, ³J 8.6 Hz), 7.82 (2H, m), 7.95 (2H, d, ³J 8.6 Hz); δ_C(67.8

MHz, CDCl₃, DEPT 90, DEPT 135) 26.63 (ϩ, CH₃), 121.17 (ϩ,

CH), 122.34 (ϩ, CH), 123.97 (ϩ, CH), 124.78 (ϩ, CH), 125.00 (ϩ,

CH), 126.34 (ϩ, CH), 129.07 (ϩ, CH), 134.80 (C_quat), 136.01 (C_quat),

138.55 (C_quat), 139.80 (C_quat), 140.06 (C_quat), 197.30 (C_quat, C᎐O); MS

᎐

(70 eV) m/z 252 (M^ϩ, 100%), 237 (M^ϩϪ CH₃, 92), 208 (36), 165 (29).

HRMS: found; 252.0606; calcd. for C₁₆H₁₂OS: 252.0609.

20 Y. Tabuchi, K. Arima and T. Thiemann, unpublished results.

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22 During the preparation of this manuscript

a similar general

procedure for carrying out Suzuki–Kumada reactions under “Jeﬀery

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and J. Dupont, Tetrahedron Lett., 2000, 41, 8199 . Here, K₃PO₄was

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hetarenes with arylboronic acids under PTC conditions interestingly

both DMF or chloroform can be used as the solvent, but

tetrabutylammonium chloride is often superior to tetrabutyl-

ammonium bromide.

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Developmental Therapeutics Program of the National Cancer

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is the synthetic equivalent to the highly strained cyclopropanone,

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2110

J. Chem. Soc., Perkin Trans. 1, 2002, 2090–2110

Article Doi

Elongated phosphoranes by C-C coupling of haloaroylmethylidene-triphenylphosphoranes: Synthesis and applications

DOI: 10.1039/b202745n

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Full text of DOI:10.1039/b202745n

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