Chalcogen electrophile induced rearrangement of 1-alkynyltrialkyl borates: Controlled syntheses of trisubstituted olefins from 1-alkynes

TETRAHEDRON

Pergamon

Tetrahedron 57 22001) 9109±9121

Chalcogen electrophile induced rearrangement of

1-alkynyltrialkyl borates: controlled syntheses of trisubstituted

ole®ns from 1-alkynes

p

Â Â

Julien Gerard and Laszlo Hevesi

Â Â

Departement de Chimie, Facultes Universitaires Notre-Dame de la Paix, 61, rue de Bruxelles, B-5000 Namur, Belgium

Received 31 May 2001; accepted 6 September 2001

AbstractÐThe reaction of 1-alkynyltrialkyl borates with sulfenyl, selenenyl and tellurenyl halides produces b-chalcogeno alkenylboranes

in good yields, with a cis relationship between the boron and the chalcogen moities. Protodeborylation of these compounds by acetic acid, or

by a transmetalation±protonolysis sequence, leads to vinyl chalcogenides, which can be converted to alkenes by means of a nickel catalyzed

coupling with Grignard reagents. Since the last two steps occur with retention of the stereochemistry, the overall sequence represents a highly

1. Introduction

borate⁷induce the rearrangement in such a way that the

migrating group of the starting 1-alkynyltrialkyl borates

and the entering electrophile end up on opposite 2trans)

sides of the emerging vinylboranes.

A fair number of methods have become available for the

generation of variously substituted vinylmetallic inter-

mediates.¹One of these methods, i.e. the electrophile

induced rearrangement of 1-alkynyltrialkyl borates 1,²

leads to vinylboranes that have proved to be quite versatile

intermediates in organic synthesis³2Scheme 1). However, it

has appeared that, depending on the electrophile used to

trigger the rearrangement, the alkenylboranes formed can

be stereochemically homogeneous or mixtures of stereo-

isomers. This in turn is most relevant to the stereochemistry

of the ®nal ole®nic product and to the synthetic usefulness

of the whole process.

On the other hand, rearrangements mediated by some so

called `complex' alkylating agents⁸like propargyl bromide,

iodoacetonitrile, a-bromo ketones and esters, as well as

2-alkyl-1,3-dioxolanium salts⁹lead to the reverse double

bond con®guration. Still other electrophiles, such as the

proton of carboxylic acids¹⁰and common alkylating

agents¹¹produce mixtures of ole®ns after protodeborylation

of the intermediate alkenylboranes, the reactions of

thexyldialkylalkynyl borates being considerably more

stereoselective.¹²

It has been shown that electrophiles like trimethylchloro-

silane,⁴dialkylchloroboranes,^2atrialkyltin chlorides,⁵

benzeneselenenyl chloride,^5a,6benzodithiolium tetra¯uoro-

Even though chalcogen electrophiles are known to react

with ole®nic and acetylenic systems, they have not

Scheme 1.

Keywords: ole®n synthesis; alkynyltrialkyl borate; rearrangement; vinyl boranes; vinyl sulphides; vinyl selenides; vinyl tellurides.

Corresponding author. Tel.: 132-81-724538; fax: 132-81-724530; e-mail: laszlo.hevesi@fundp.ac.be

p

PII: S0040-4020201)00904-8

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J. Gerard, L. Hevesi / Tetrahedron 57 ,2001) 9109±9121

attracted much attention in relation with the rearrangement

of 1-alkynyltrialkyl borate salts. Hooz and Mortimer have

reported that the reaction of lithium 1-hexynyltriethyl borate

with benzenesulfenyl chloride led to a stereoisomeric

mixture of vinyl sul®des after hydrolysis,^5awhereas the

reaction of lithium 1-hexynyltricyclopentyl borate with

benzeneselenenyl chloride was suggested to place the

migrating cyclopentyl and the entering selenenyl groups

trans to each other.⁶

1-2phenyltelluro)-1-heptyne, as well as n-pentylcyclohexyl-

acetylene could be detected in the corresponding crude

products 2Scheme 2, entries 4 and 5).

Furthermore, it has appeared for the ®rst time that tellurenyl

halides¹⁴can induce the reaction with comparable ef®ciency

2Scheme 2, entry 5) to that of their sulfenyl and selenenyl

analogs. The interesting chemistry of vinyl tellurides

described in recent years¹⁵confers particular signi®cance

to this ®nding.

Therefore, we have decided to reinvestigate more

thoroughly the title reaction in the presence of chalcogen

electrophiles with the primary aim of ascertaining its stereo-

chemistry. Additionally, we felt that the now well docu-

mented transition metal catalyzed reactions of the vinylic

intermediates ¯anked by two different heteroatomic

moieties should allow to construct highly substituted

alkenes in a fully controlled fashion.

Good quality monocrystals of compounds 2b±e could be

grown from chloroform solutions, which allowed us to

determine their structure by X-ray crystallography.¹⁶Most

gratifyingly, in all four cases the migrating alkyl group and

entering chalcogen moiety exhibit trans stereochemical

relationships 2as depicted in Scheme 2). This is an important

starting point for our inquiry of the synthetic usefulness of

the rearrangement.

In this paper we wish to report details of our results on the

highly regio- and stereoselective synthesis of trisubstituted

ole®ns¹³using this methodology.

In subsequent work we have not attempted to isolate the

intermediate vinylic boron-chalcogen compounds 2;

instead, we have subjected them to protodeborylation in a

one pot sequence leading to the 1,2-disubstituted vinyl

chalcogenides 2sul®des, selenides, tellurides) 3.

2. Results and discussion

It can be seen in Scheme 3 that as long as R²is a primary

alkyl group, all the alkenylboranes readily underwent

protonolysis of the carbon±boron bond by means of acetic

acid, whereas those bearing secondary alkyl or cycloalkyl

groups on boron appeared very resistant to protonolysis.

Thus, re¯uxing alkenylborane 2b overnight in THF in the

presence of 3 equiv. of acetic acid left it essentially

unchanged. This observation, as well as similar ones made

by others¹⁷contrast with the reportedly easy and ef®cient

protonolysis of analogous a-halogeno alkenylboranes.¹⁸

In view of establishing their ef®ciency and stereochemical

outcome, the rearrangements of various 1-alkynyltrialkyl

borates have been carried out in the presence of different

chalcogenyl halides 2S, Se, Te). As shown in Scheme 2, the

reactions proceeded smoothly under mild conditions.

The yields stated are those in puri®ed products 2by column

chromatography or by distillation). Vinylic boron-chalco-

gene derivatives 2a±e are stable crystalline solids; 2f is a

stable liquid, and 2g is an unstable, air-sensitive liquid. It is

also noteworthy that in all cases the rearrangement occurred

cleanly; side reactions such as 2i) a-attack of the electro-

philes on the triple bond, 2ii) attack on the R²groups or

2iii) syn elimination leading to internal alkynes R¹±CC±

R²have not been observed or have taken place to negligible

extents. Thus, only trace amounts of 1-2phenylseleno)- and

In spite of its ef®ciency, protodeborylation of b-

2phenylthio)- and b-2butylthio) alkenylboranes 2 2R²

primary alkyl) was found extremely sensitive to the way

the work-up was conducted, in the sense that aqueous

work-up 2i.e. quenching the reaction mixture with aqueous

Scheme 2.

J. Gerard, L. Hevesi / Tetrahedron 57 ,2001) 9109±9121

9111

Scheme 3.

sodium bicarbonate) invariably led to more or less exten-

sively isomerized vinyl sul®des 3. On the contrary, when

triethylamine, or better ethanolamine¹⁹was used to quench

the reaction mixture 2see Section 3), the stereochemical

integrity of the products was completely preserved

2E/Z.98:2 in all cases). In fact, occasionally the triethyl-

amine-based procedure gave more capricious results than

that using ethanolamine. In this regard we have noticed

that in the former case the crude products still contained

large amounts of borane by-products, whereas the ethano-

lamine treatment led to crude products essentially free of

borane. This observation suggested that the borane by-

products of the acetic acid mediated protodeborylations,

namely acetoxydialkyl boranes, might have caused the

isomerization of vinyl sul®des 3. The experiments shown

in Scheme 4 lend strong support to this hypothesis;

however, we have not further investigated the mechanism

of the isomerizations. Interestingly, this problem of

isomerization during aqueous work-up was not encountered

in the protodeborylation of b-seleno- and b-telluro vinyl

derivatives 2; indeed, 2E)-5-2phenylseleno)-5-decene

appeared insensitive to the presence of acetoxydicyclo-

hexylborane 2Scheme 4e).

In as much as it can be inferred from the X-ray structures

that the rearrangements follow the same stereochemical

course in all the cases, and if the protodeborylation of

compounds 2 occurs as usual^3a,17,18with retention of

Scheme 4.

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J. Gerard, L. Hevesi / Tetrahedron 57 ,2001) 9109±9121

Scheme 5.

stereochemistry, vinyl chalcogenides 3 should have the

structures shown in Scheme 3. These assumptions have

been com®rmed by NOE measurements carried out on

2E)- and 2Z)-5-phenyl-5-decene prepared from 2E)- and

2Z)-5-2phenylthio)-5-decene, respectively 2vide infra).

alkynes 2Scheme 5, entries 4 and 5). By contrast, the b-

2phenylseleno) compound 2d led to quantitative production

of pentylcyclohexylacetylene even at 2338C 2Scheme 5,

entry 6). At lower temperatures the boron to copper trans-

metallation did not occur.

As mentioned above, the sterically hindered vinyl boranes 2

2R²secondary alkyl or cycloalkyl) were found reluctant

towards protonolysis of the C±B bond without prior activa-

tion of the boron moiety. This latter can be achieved in

several ways among which the most ef®cient one is the

boron to copper transmetallation sequence.^17,20,21A few

examples of this procedure applied to b-2phenylthio)- or

b-2butylthio) alkenylboranes are shown in Scheme 5.

The last step in the synthesis of the targetted trisubstituted

alkenes was the conversion of the vinyl chalcogenides 2S,

Se, Te) 3 into ole®ns 4.

As shown in Scheme 6, a straightforward way of doing this

conversion is the now well documented²²nickel catalyzed

coupling of 3 with Grignard reagents. Even though the over-

all results are quite satisfactory, these transformations, like

other transition metal catalyzed coupling reactions, have

appeared very sensitive to the structure of the phosphine

ligand. It was found initially^22a,bthat bis2triphenylphos-

phino)nickel chloride was an appropriate catalyst precursor;

however, later work has revealed that ligands such as bis-

2diphenylphosphino)ethane 2dppe) and bis2diphenyl-

phosphino)propane 2dppp) gave higher yields and better

stereoselectivities.^22c±eOur observation is also that dppe is

a good ligand for all the couplings involving vinyl sul®des

2Scheme 6, entries 1±7). One can notice, however, that

different relative amounts of Grignard reagents may be

necessary to obtain satisfactory yields. Thus, while the

couplings of phenylvinyl sul®des with phenylmagnesium

bromide required at least 2 equiv. of the latter reagent^22a

2Scheme 6, entries 1±4), the reaction of butylvinyl sul®de

with 1.5 equiv. of phenylmagnesium bromide took place

with excellent yield 2Scheme 6, entry 5). Nevertheless,

coupling of the same butylvinyl sul®de occurred ef®ciently

only in the presence of a large excess of butylmagnesium

bromide 2Scheme 6, entries 6 and 7).

Two factors have appeared to play an important role in

the ef®ciency of this process; both of them are related to

the syn elimination of the boron and chalcogen moieties

producing the undesired internal alkynes R¹±CC±R². This

elimination can take place either at the stage of the ®rst

formed

b-chalcogeno

alkenylborate

intermediates

2eventually in equilibrium with the corresponding vinyl-

lithiums), or at the next formed b-chalcogeno alkenylcopper

2or cuprate) derivatives. In any event, it proceeds faster at

higher temperatures and with better chalcogen leaving

groups. Thus, in the case of b-2phenylthio) alkenylborane

2a decreasing the reaction temperature to 2338C leads to

substantial increase in the yields of vinyl sul®de 3a and to a

concomitant decrease in the yields of the elimination

product, that is butylcyclohexylacetylene 2Scheme 5, entries

1±3). Due to the lower propensity of the b-2butylthio)

derivatives 2c and 2f to undergo the syn elimination

reactions, their protodeborylations took place in high yields

at 2238C without formation of the corresponding internal

J. Gerard, L. Hevesi / Tetrahedron 57 ,2001) 9109±9121

9113

Scheme 6.

Regarding the nickel catalyzed coupling process, vinyl

selenides and tellurides display much similarity to vinyl

sul®des.^22j±pIn agreement with earlier ®ndings^22jby Takei

et al. we have observed for the coupling of phenylvinyl

selenides: 2i) ef®cient reaction with PhMgBr in the presence

of NiCl₂2PPh₃)₂2Scheme 6, entry 8). This catalyst has also

been found to perform satisfactorily in the couplings of

methylvinyl selenides with trimethylsilylmethylmagnesium

chloride^22k2but in those cases use of dimethoxyethane as

solvent was necessary). 2ii) while NiCl₂2dppe) was totally

ineffective for the reaction with methylmagnesium bromide,

the coupling took place in the presence of NiCl₂2dppp)

2Scheme 6, entries 9,10). 2iii) The reaction with butyl-

magnesium bromide gave low yields 2Scheme 6, entry 11)

even in the presence of NiCl₂2dppp), in spite of the

reportedly good performance^22jof this catalyst under

comparable circumstances. Presumably, in this case the

undesired b-hydride elimination at the Ni-butyl moiety is

an ef®cient competitor of the coupling reaction.

also Section 3) are 2i) for 2E)-5-phenyl-5-decene 4a:

5.63 ppm 2t, J7.3 Hz, ole®nic proton), 2.48 ppm 2t,

J7.1 Hz, allylic CH₂trans to the ole®nic proton),

2.19 ppm 2q, J7.3 Hz, allylic CH₂trans to the phenyl

group) and 2ii) for 2Z)-5-phenyl-5-decene 4a⁰: 5.42 ppm 2t,

J7.3 Hz, ole®nic proton), 2.31 ppm 2t, J7.0 Hz, allylic

CH₂cis to the ole®nic proton), 1.91 ppm 2q, J7.3 Hz,

allylic CH₂cis to the phenyl group). In the DiffNOE spec-

trum 2resulting from irradiation of the ole®nic proton) of the

former compound all signals vanish except those of the

phenyl multiplet and of the allylic quartet, witnessing for

the 2E) stereochemistry of the double bond, whereas the

same kind of difference spectrum of the latter ole®n

shows only the two allylic multiplets, indicating 2Z) stereo-

chemistry.

Finally, vinyl tellurides have been converted into the target

ole®ns in two ways: 2i) phenylvinyl tellurides such as 3n

2Scheme 3) smoothly underwent the nickel catalyzed

coupling with Grignard reagents^22m,n2Scheme 6, entry

12), and 2ii) based on extensive studies of tellurium±metal

At this stage it was appropriate to check the structure of

ole®ns 4, especially their stereochemistry. This has been

done by NMR spectroscopy 2DiffNOE technique) in the

case of 5-phenyl-5-decene. The 2E) and 2Z) stereoisomers

of this ole®n have been prepared from 2E)- and 2Z)-5-

2phenylthio)-5-decene 3h and 3h⁰2themselves obtained

through protodeborylation of the intermediate with acetic

acid followed by aqueous work-up 2Method B; see Section

3), and chromatographic separation), respectively, accord-

ing to Scheme 7.

The characteristic ¹H NMR resonances of these ole®ns 2see

Scheme 7.

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J. Gerard, L. Hevesi / Tetrahedron 57 ,2001) 9109±9121

Scheme 8.

exchange reactions,¹⁵butylvinyl telluride 3o have been

transformed into functionalized ole®ns 5 and 6 according

to Scheme 8.

1208C for several hours prior to use. The glasswares were

assembled while hot and cooled under a stream of argon.

Melting points were recorded on an Electrothermal 9100

1

apparatus and are uncorrected. H 2400 and 90 MHz) and

It has been shown by Comasseto and coworkers that, on

treatment with butyllithium, arylvinyl tellurides gave

mixtures of aryl- and vinyllithiums, whereas under similar

conditions alkylvinyl tellurides produce the corresponding

vinyllithiums in good yields and with retention of stereo-

chemistry.^15a,dIn our case, the vinyllithium formed from 3o

gave the allylic alcohols 5a and 5b in good yields on

reaction with benzaldehyde and cyclohexanone, respec-

tively 2Scheme 8, Path A). On the other hand, cleavage of

the C_vinyl±Te bond of 3o by means of a higher order cyano-

cuprate^{15c,d,f±i,23}gave the corresponding vinylcuprate which

underwent clean Michael additions to a,b-unsaturated

ketones to produce g,d-unsaturated ketones 6a±c 2Scheme

8, Path B).

¹³C 2100.4 and 22.5 MHz) NMR spectra were recorded on

either a JEOL JNM EX-400 or a JEOL JNM EX-90 with

CDCl₃as solvent and Me₄Si as internal standard. IR spectra

were recorded on a BIORAD FTS-165 spectrometer.

Elemental analysis were carried out using a Carlo-Erba

NA 1500 C, H, N analyser. Low resolution mass measure-

ments were carried out using a Hewlett±Packard HP6890

GC-MS instrument 2ionization potential: 70 eV); relative

intensities of the ions are given in parentheses. High resolu-

tion mass spectra were recorded on a Micromass AutoSpec

6F mass spectrometer. Merck silica gel 9385 20.040±

0.063 mm) and 5111 20.015±0.040 mm) and Aldrich basic

aluminum oxide 2,150 mesh) were used for column

chromatography. THF and Et₂O were distilled from

sodium/benzophenone. HMPA was distilled from CaH₂.

1-Hexyne, 1-heptyne, phenylacetylene, 3-butyn-1-ol,

5-bromo-1-pentene, benzaldehyde, cyclohexanone, cyclo-

hexenone, methyl vinyl ketone, 2R)-22)-carvone and thio-

phene were purchased from Aldrich and distilled prior to

use. The other reagents were purchased from Aldrich and

used without further puri®cation, except trihexylborane,

tricyclohexylborane, benzenesulfenyl chloride, butyl-

sulfenyl chloride, phenyltellurenyl iodide, butyltellurenyl

iodide and 4-22tetrahydropyranyl)oxy)-1-butyne, which

were synthesized according to the reported procedures.

In conclusion, the great stereoselectivity of the title process

combined with an appropriate choice of reagent at each step

leads to a ¯exible trisubstituted ole®n synthesis.

3. Experimental

3.1. General

All glassware, syringes and needles were oven dried at

J. Gerard, L. Hevesi / Tetrahedron 57 ,2001) 9109±9121

9115

3.1.1. Representative procedure for the synthesis of

secondary dialkyl alkenyl boranes. Preparation of +E)-

1-cyclohexyl-1-+dicyclohexylboryl)-2-+phenylthio)-1-

hexene +2a). A 100 ml two-necked ¯ask, equipped with an

argon inlet and a magnetic stirring bar, was charged with a

THF solution 215 ml) of 1-hexyne 20.822 g; 10 mmol).

n-Butyllithium 26.25 ml of a 1.6 M solution in hexane;

10 mmol) was added at 2208C. After 1 h of stirring at

2208C, freshly prepared tricyclohexylborane 220 ml of a

0.5 M solution in THF; 10 mmol) was introduced and the

reaction mixture was allowed to warm to room temperature

for 1 h. After cooling to 2788C, a THF solution 220 ml) of

benzenesulfenyl chloride 21.445 g; 10 mmol) was added

dropwise. The cooling bath was then removed and the

mixture was stirred for 30 min at room temperature. The

solution was diluted with 50 ml of Et₂O, washed with

water, dried over MgSO₄, and concentrated. The crude

product was puri®ed by column chromatography 2silica

gel; pentane) to afford 3.205 g 271% yield) of 2a as a

viscous colorless liquid, which crystallized on standing.

Mp 70±728C; IR 2KBr): 3061, 2926, 2851, 1584, 1478,

3.1.4. +E)-1-Cyclohexyl-1-+dicyclohexylboryl)-2-+phenyl-

seleno)-1-heptene +2d). The same procedure as for the

preparation of 2a was duplicated, using 1-heptyne and

phenylselenenyl chloride. Column chromatography 2silica

gel; pentane) afforded 2d as a white solid 272% yield)

which could be recrystallized from CHCl₃. Mp 100±

1018C; IR 2KBr): 3059, 2926, 2847, 2776, 1580, 1477,

1

1445, 732, 689 cm²¹; H NMR 2400 MHz, CDCl₃): d 0.87

23H, t, J6.8 Hz), 1.07±1.31 221H, m), 1.50±1.86 217H,

m), 2.33 22H, t, J7.6 Hz), 2.37 21H, m), 7.14±7.31 25H,

m); ¹³C NMR 2100 MHz, CDCl₃): d 14.1, 22.6, 26.2, 26.9,

27.1, 28.3, 28.6, 29.1, 30.2, 30.3, 31.4, 32.3, 32.7, 36.1,

43.2, 122.5, 126.0, 128.8, 130.0, 132.8, 167.8; MS 2EI):

512 2M¹, 2), 429 263), 347 221), 240 239), 189 238), 158

288), 55 2100); Anal. Calcd for C₃₁H₄₉BSe: C, 72.79; H,

9.66. Found: C, 73.53; H, 9.53.

3.1.5. +E)-1-Cyclohexyl-1-+dicyclohexylboryl)-2-+phenyl-

telluro)-1-heptene +2e). The same procedure as for the

preparation of 2a was duplicated, using 1-heptyne and

phenyltellurenyl iodide. Column chromatography 2silica

gel; pentane) afforded 2e as a pale yellow solid 269%

yield) which could be recrystallized from CHCl₃. Mp 98±

998C; IR 2KBr): 3055, 2926, 2846, 2774, 1575, 1474, 1443,

725, 690 cm²¹; ¹H NMR 2400 MHz, CDCl₃): d 0.88 23H, t,

J6.8 Hz), 1.08±1.33 221H, m), 1.50±1.89 217H, m), 2.39±

2.43 23H, m), 7.17 23H, m), 7.47 22H, m); ¹³C NMR

222.5 MHz, CDCl₃):d 14.1, 22.6, 26.3, 27.0, 27.2, 28.3,

28.7, 30.2, 30.9, 31.1, 31.2, 32.8, 34.6, 35.8, 45.3, 111.1,

116.9, 126.9, 129.0, 135.2; MS 2EI): 562 2M¹, 16), 479

2100), 395 217), 273 234), 265 222), 189 210), 179 229),

195 210), 83 210); Anal. Calcd for C₃₁H₄₉BTe: C, 66.47;

H, 8.82. Found: C, 67.18; H, 9.02.

1446, 738, 692 cm²^{1 1}H NMR 2400 MHz, CDCl₃): d

;

0.87 23H, t, J6.8 Hz), 1.05±1.35 219H, m), 1.45±1.86

217H, m), 2.25 22H, t, J7.8 Hz), 2.36 21H, m), 7.11±

7.26 25H, m); ¹³C NMR 2100 MHz, CDCl₃): d 14.0,

22.4, 26.2, 26.8, 27.1, 28.3, 28.5, 29.7, 29.9, 30.4,

31.1, 32.6, 36.0, 42.3, 123.3, 125.4, 127.5, 128.5,

136.9; MS 2EI): 450 2M¹, 3), 367 2100), 361 222),

285 248), 279 211), 257 26), 203 216), 175 213), 135

212), 55 28).

3.1.2. +E)-1-Cyclohexyl-1-+dicyclohexylboryl)-2-+phenyl-

thio)-1-heptene +2b). The same procedure as for the

preparation of 2a was duplicated, using 1-heptyne. Column

chromatography 2silica gel; pentane) afforded 2b as a white

solid 284% yield) which could be recrystallized from

CHCl₃. Mp 85±868C; IR 2KBr): 3060, 2924, 2846, 2776,

3.1.6. +E)-4-+Di-sec-butylboryl)-5-+butylthio)-3-methyl-

4-nonene +2f). The same procedure as for the preparation

of 2a was duplicated, using tri-sec-butylborane and butyl-

sulfenyl chloride. Column chromatography 2silica gel;

pentane) afforded 2f as a viscous colorless liquid in 80%

yield. IR 2neat): 2960, 2931, 2870, 1563, 1461, 1376,

1

1584, 1478, 1444, 735, 688 cm²¹; H NMR 2400 MHz,

CDCl₃): d 0.86 23H, t, J6.8 Hz), 1.09±1.29 221H, m),

1.46±1.86 217H, m), 2.24 22H, t, J7.8 Hz), 2.36 21H,

m), 7.10±7.26 25H, m); ¹³C NMR 2100 MHz, CDCl₃): d

14.1, 22.5, 26.2, 26.8, 27.1, 28.3, 28.5, 28.5, 29.7, 29.9,

30.5, 31.5, 32.6, 36.0, 42.3, 123.3, 125.4, 127.6, 128.5,

136.9, 168.6; MS 2EI): 464 2M¹, 4), 381 2100), 299 296),

271 223), 217 234), 189 251), 135 259), 121 231), 55 234);

Anal. Calcd for C₃₁H₄₉BS: C, 80.14; H, 10.63. Found: C,

80.00; H, 10.81.

994 cm²^{1 1}H NMR 2400 MHz, CDCl₃): d 0.88±1.25

;

230H, m), 1.38 24H, m), 1.52 24H, m), 1.58±1.76 22H, m),

2.14±2.32 23H, m), 2.55 22H, t, J7.4 Hz); ¹³C NMR

222.5 MHz, CDCl₃): d 12.7, 13.7, 14.0, 14.2, 15.5, 15.7,

16.0, 18.7, 18.8, 22.3, 22.5, 26.7, 26.8, 29.5, 29.6, 29.9,

30.6, 31.5, 33.3, 38.0, 126.6; MS 2EI): 352 2M¹, 1), 295

2100), 239 284), 205 210), 183 218), 149 215), 115 215), 57

220); HRMS 2CI): m/z for C₂₂H₄₆BS, Calcd: 353.3413.

Found: 353.3411.

3.1.3.

+E)-2-+Butylthio)-1-cyclohexyl-1-+dicyclohexyl-

boryl)-1-heptene +2c). The same procedure as for the

preparation of 2a was duplicated, using 1-heptyne and

butylsulfenyl chloride. Column chromatography 2silica

gel; pentane) afforded 2c as a white solid 272% yield)

which could be recrystallized from CHCl₃. Mp 56±578C;

3.1.7. +E)-3-+Diethylboryl)-4-+phenylthio)-3-octene +2g).

A 50 ml two-necked ¯ask, equipped with an argon inlet

and a magnetic stirring bar, was charged with a THF solu-

tion 210 ml) of 1-hexyne 20.657 g; 8 mmol). At 2208C were

added 5 ml of n-butyllithium 21.6 M in hexane; 8 mmol).

After 1 h of stirring at 2208C, 8 ml of triethylborane 21 M

solution in THF; 8 mmol) were introduced and the reaction

mixture was allowed to warm to room temperature for 1 h.

After cooling to 2788C, a THF solution 210 ml) of benzene-

sulfenyl chloride 21.156 g; 8 mmol) was added dropwise.

The cooling bath was then removed and the mixture was

stirred for 30 min at room temperature. After removal of the

solvents under reduced pressure, the residue was extracted

1

IR 2KBr): 2919, 2846, 2769, 1600, 1444 cm²¹; H NMR

290 MHz, CDCl₃): d 0.90 26H, m), 1.15±1.69 242H, m),

2.10±2.27 23H, m), 2.53 22H, t, J7.1 Hz); ¹³C NMR

222.5 MHz, CDCl₃):d 13.7, 14.1, 22.2, 22.6, 26.3, 26.9,

27.4, 28.1, 28.5, 28.8, 29.8, 30.0, 30.5, 31.5, 31.6, 32.7,

33.6, 34.9, 41.6, 126.0, 162.8; MS 2EI): 444 2M¹, 3), 361

2100), 279 247), 271 28), 189 215), 149 28), 83 26), 57 27);

Anal. Calcd for C₂₉H₅₃BS: C, 78.34; H, 12.01. Found: C,

78.08; H, 12.67.

9116

J. Gerard, L. Hevesi / Tetrahedron 57 ,2001) 9109±9121

with pentane 2ca. 2£5 ml) via a syringe, the extracts being

collected in a 25 ml, argon ¯ushed ¯ask, equipped with an

argon inlet. The pentane was then removed under vacuum,

and the residue was directly distilled in a Kugelrohr

apparatus under reduced pressure 2bp 120±1308C at

0.2 mm Hg), giving 1.808 g of 2g 279% yield) as a colorless

liquid. ¹H NMR 2400 MHz, CDCl₃): d 0.87 23H, t,

J7.3 Hz), 0.91 26H, t, J7.8 Hz), 1.00 23H, t,

J7.5 Hz), 1.15 24H, q, J7.8 Hz), 1.29 22H, m), 1.48

22H, m), 2.21 22H, t, J7.5 Hz), 2.25 22H, q, J7.5 Hz),

7.11±7.15 21H, m), 7.19±7.30 24H, m).

Calcd for C₁₆H₂₄S: C, 77.36; H, 9.74. Found: C, 77.60; H,

10.16.

3.1.10. +E)-1-Phenyl-1-+phenylthio)-1-butene +3i). The

same procedure as for the preparation of 3g was duplicated,

using phenylacetylene. 3i was obtained as a colorless liquid

in 70% yield. This compound spontaneously isomerized on

standing at room temperature. IR 2neat): 3076, 3058, 3020,

2967, 2931, 2873, 1583, 1478, 1440, 1071, 1025, 762, 741,

699 cm²^{1 1}H NMR 290 MHz, CDCl₃): d 0.99 23H, t,

;

J7.3 Hz), 2.15 22H, quint., J7.5 Hz), 6.13 21H, t,

J7.5 Hz), 7.04±7.39 210H, m); ¹³C NMR 222.5 MHz,

CDCl₃): d 14.2, 23.7, 126.3, 127.4, 127.9, 128.6, 129.3,

130.3, 133.3, 135.2, 138.1, 138.3; MS 2EI): 240 2M¹,

100), 211 233), 131 273), 121 227), 115 242), 91 259), 77

216); HRMS: m/z for C₁₆H₁₆S, Calcd: 240.0973. Found:

240.0970.

3.1.8. Representative procedure for the protodeboryl-

ation of alkenyl boranes with acetic acid +Method A).

Preparation of +E)-4-+phenylthio)-3-octene +3g).

A

50 ml two-necked ¯ask under an argon atmosphere, contain-

ing a stirred solution of 1-hexyne 20.197 g; 2.4 mmol) in

THF 24 ml), was cooled to 2208C. n-Butyllithium 21.5 ml

of a 1.6 M solution in hexane; 2.4 mmol) was added, and the

reaction mixture was stirred for 1 h at 2208C. Triethyl-

borane 22.4 ml of a 1 M solution in THF; 2.4 mmol) was

introduced and the reaction mixture was allowed to warm to

room temperature. After 1 h of stirring, the ¯ask was cooled

to 2788C and a solution of benzenesulfenyl chloride

20.347 g; 2.4 mmol) in THF 23 ml) was added dropwise.

The reaction mixture was allowed to warm to room

temperature, charged with 20 ml of Et₂O, and a solution

of acetic acid 20.317 g; 4.8 mmol; 2.2 equiv.) in Et₂O

22 ml) was introduced. After 1 h of stirring, 1 ml of ethano-

lamine 216.6 mmol; 7 equiv.) was added, giving rise to a

biphasic system, and the mixture was vigourously stirred

for 15 min. The two layers were then separated, the ethereal

one was concentrated, and the pale yellow liquid residue

was extracted with pentane 23£15 ml). The combined

pentane layers were dried over sodium carbonate, and

concentrated. The crude product was puri®ed by column

chromatography 2basic alumina; pentane) to give 0.390 g

of 3g 274% yield) as a colorless liquid. IR 2neat): 3072,

2962, 2932, 2873, 1584, 1477, 1440, 1378, 1151, 1088,

3.1.11. +E)-1-[+Tetrahydropyran-2-yl)oxy]-3-phenylthio-

3-hexene +3j). The same procedure as for the preparation of

3g was duplicated, using 4-[2tetrahydropyran-2-yl)oxy]-1-

butyne. 3j was obtained as a colorless liquid in 69% yield.

IR 2neat): 3059, 2943, 2873, 1584, 1477, 1440, 1351, 1202,

1136, 1121, 1068, 1034, 990, 870, 742, 693 cm²¹; ¹H NMR

2400 MHz, CDCl₃): d 1.03 23H, t, J7.3 Hz), 1.47±1.80

26H, m), 2.21 22H, quint., J7.3 Hz), 2.50 22H, m), 3.50

22H, m), 3.83 22H, m), 4.55 21H, br s), 5.99 21H, t,

J7.3 Hz), 7.16±7.20 21H, m), 7.25±7.32 24H, m); ¹³C

NMR 222.5 MHz, CDCl₃): d 14.0, 19.4, 22.6, 25.4, 30.6,

31.7, 62.1, 65.6, 98.7, 126.2, 128.8, 129.3, 129.7, 135.8,

141.1; MS 2EI): 292 2M¹, 6), 208 210), 183 214), 159

218), 135 27), 110 213), 85 2100), 67 215); HRMS: m/z for

C₁₇H₂₄O₂S, Calcd: 292.1497. Found: 292.1504.

3.1.12. +E)-4-+Butylthio)-3-nonene +3k). The same pro-

cedure as for the preparation of 3g was duplicated, using

1-heptyne and butylsulfenyl chloride. 3k was obtained as a

colorless liquid in 83% yield. IR 2neat): 2961, 2931, 2873,

1

2861, 1624, 1462, 1379, 1152, 886, 732 cm²¹; H NMR

1

1025, 741, 692 cm²¹; H NMR 2400 MHz, CDCl₃): d 0.86

290 MHz, CDCl₃): d 0.82±1.06 29H, m), 1.15±1.66 210H,

m), 2.10 24H, m), 2.63 22H, t, J7.0 Hz), 5.31 21H, t,

J7.2 Hz); ¹³C NMR 222.5 MHz, CDCl₃): d 13.7, 14.0,

14.5, 22.0, 22.1, 22.5, 28.6, 30.8, 31.1, 31.6, 31.7, 127.8,

134.2; MS 2EI): 214 2M¹, 49), 171 29), 157 2100), 115 249),

102 263), 81 231), 69 235), 55 231); HRMS: m/z for C₁₃H₂₆S,

Calcd: 214.1755. Found: 220.1750.

23H, t, J7.0 Hz), 1.02 23H, t, J7.3 Hz), 1.27 22H, m),

1.47 22H, m), 2.15 22H, quint., J7.3 Hz), 2.18 22H, t,

J7.3 Hz), 5.84 21H, t, J7.3 Hz), 7.15±7.20 21H, m),

7.25±7.32 24H, m); ¹³C NMR 2100 MHz, CDCl₃): d 13.9,

14.1, 22.3, 22.5, 30.8, 126.1, 128.8, 129.9, 133.2, 135.9,

138.5; MS 2EI): 220 2M¹, 78), 178 269), 150 2100), 135

278), 110 248), 69 234), 55 230); HRMS: m/z for C₁₄H₂₀S,

Calcd: 220.1286. Found: 220.1287.

3.1.13. Representative procedure for the protodeboryl-

ation of alkenyl boranes with acetic acid +Method B).

Preparation of +E)-6-+phenylseleno)-6-tridecene +3l). A

50 ml two-necked ¯ask under an argon atmosphere, contain-

ing a stirred solution of 1-heptyne 20.577 g; 6 mmol) in THF

29 ml), was cooled to 2208C. n-Butyllithium 23.75 ml of a

1.6 M solution in hexane; 6 mmol) was added, and the reac-

tion mixture was stirred for 1 h at 2208C. Trihexylborane

210 ml of a 0.6 M solution in THF; 6 mmol) was introduced

and the reaction mixture was allowed to warm to room

temperature. After 1 h of stirring, the ¯ask was cooled to

2788C and a solution of phenylselenenyl chloride 21.149 g;

6 mmol) in THF 28 ml) was added dropwise. The reaction

mixture was allowed to warm to room temperature and

acetic acid 21.03 ml; 18 mmol; 3 equiv.) was introduced.

After 1 h of stirring, the mixture was diluted with Et₂O

3.1.9. +E)-5-+Phenylthio)-5-decene +3h). The same pro-

cedure as for the preparation of 3g was repeated, using

tributylborane, except that the mixture was heated at 608C

for 1 h after the introduction of acetic acid. 3h was obtained

as a colorless liquid in 73% yield. IR 2neat): 3068, 2958,

2930, 2864, 1584, 1477, 1440, 1379, 1150, 1090, 1025, 740,

1

692 cm²¹; H NMR 2400 MHz, CDCl₃): d 0.86 23H, t,

J7.3 Hz), 0.92 23H, t, J7.0 Hz), 1.27 22H, m), 1.31±

1.41 24H, m), 1.47 22H, m), 2.15 24H, m), 5.85 21H, t,

J7.5 Hz), 7.16±7.20 21H, m), 7.25±7.31 24H, m); ¹³C

NMR 2100 MHz, CDCl₃): d 13.9, 22.3, 22.4, 28.8, 30.8,

30.9, 31.6, 126.1, 128.8, 129.9, 133.6, 136.1, 137.1; MS

2EI): 248 2M¹, 83), 205 239), 150 2100), 135 257), 123

225), 110 235), 97 225), 83 227), 67 225), 55 230); Anal.

J. Gerard, L. Hevesi / Tetrahedron 57 ,2001) 9109±9121

9117

230 ml), washed with saturated aqueous NaHCO₃and with

water, dried over MgSO₄and concentrated. The crude

product was puri®ed by column chromatography 2silica

gel; pentane) to give 1.323 g of 3l 265% yield) as a pale

yellow liquid. IR 2neat): 3071, 2958, 2928, 2857, 1580,

110 29), 81 211), 69 2100), 55 254); HRMS: m/z for

C₁₂H₂₄Te, Calcd: 298.0940. Found: 298.0945.

3.1.17. +Z)-5-+Phenylthio)-5-decene +3h⁰). The same

procedure as for the preparation of 3l was duplicated,

using 1-hexyne, tributylborane and benzenesulfenyl chlo-

ride. Analysis of the crude product revealed the presence

of two stereoisomers that could be separated by column

chromatography 2silica gel; pentane). 2E)- and 2Z)-5-

2phenylthio)-5-decene 23h and 3h⁰) were obtained as

colorless liquids in 42 and 27%, respectively. 3h⁰: IR

2neat): 3073, 2958, 2928, 2858, 1584, 1477, 1465, 1439,

1

1465, 1439, 1378, 1068, 1023, 735, 691, 669 cm²¹; H

NMR 2400 MHz, CDCl₃): d 0.87 26H, m), 1.20±1.51

214H, m), 2.11 22H, q, J7.3 Hz), 2.24 22H, t, J7.5 Hz),

5.94 21H, t, J7.3 Hz), 7.21±7.27 23H, m), 7.45 22H, m);

¹³C NMR 222.5 MHz, CDCl₃): d 14.0, 14.1, 22.5, 22.6, 28.6,

28.9, 29.4, 31.3, 31.7, 32.9, 126.6, 128.9, 131.2, 131.9,

132.4, 138.5; MS 2EI): 338 2M¹, 75), 307 244), 275 215),

243 211), 198 245), 158 243), 111 227), 97 249), 83 257), 69

2100), 55 291); HRMS: m/z for C₁₉H₃₀Se, Calcd: 338.1513.

Found: 338.1509.

1

1379, 1094, 1025, 739, 692 cm²¹; H NMR 2400 MHz,

CDCl₃): d 0.84 23H, t, J7.3 Hz), 0.90 23H, t, J7.1 Hz),

1.22 22H, m), 1.32±1.41 24H, m), 1.45 22H, m), 2.15 22H, t,

J7.8 Hz), 2.33 22H, t, J7.2 Hz), 5.89 21H, t, J7.1 Hz),

7.14±7.18 21H, m), 7.23±7.30 24H, m); ¹³C NMR

2100 MHz, CDCl₃): d 13.9, 14.0, 21.9, 22.3, 29.6, 30.7,

31.6, 37.2, 125.6, 128.7, 129.2, 133.1, 135.8, 136.7; MS

2EI): 248 2M¹, 77), 205 236), 150 2100), 135 252), 123

224), 110 236), 97 226), 83 229), 67 225), 55 234).

3.1.14. +E)-5-+Phenylseleno)-5-decene +3m). The same

procedure as for the preparation of 3l was duplicated,

using 1-hexyne and tributylborane. 3m was obtained as a

pale yellow liquid in 81% yield. IR 2neat): 3071, 2958,

2929, 2871, 1580, 1475, 1438, 1379, 1023, 735,

1

691 cm²¹; H NMR 290 MHz, CDCl₃): d 0.80±0.98 26H,

m), 1.15±1.56 28H, m), 2.17 24H, m), 5.94 21H, t,

J7.3 Hz), 7.19±7.52 25H, m); ¹³C NMR 222.5 MHz,

CDCl₃): d 13.9, 22.2, 22.3, 29.2, 31.1, 31.6, 32.6, 126.6,

129.0, 131.1, 131.8, 132.4, 138.4; MS 2EI): 296 2M¹, 98),

253 28), 198 253), 183 220), 158 253), 129 217), 117 213),

97 247), 83 258), 69 240), 55 2100); HRMS: m/z for

C₁₆H₂₄Se, Calcd: 296.1043. Found: 296.1042; Anal.

Calcd for C₁₆H₂₄Se: C, 65.07; H, 8.19. Found: C, 64.72;

H, 8.34.

3.1.18. Representative procedure for the protodeboryl-

ation of thio-alkenyl boranes by means of the activation±

transmetallation±protonolysis sequence. Preparation of

+E)-1-cyclohexyl-2-+phenylthio)-1-hexene +3a). In a 25 ml

two-necked ¯ask, equipped with an argon inlet and a

magnetic stirring bar, were introduced a THF solution

23 ml) of 2a 20.410 g; 0.91 mmol) and 0.45 ml of HMPA.

Methyllithium was added at 2338C 21.3 ml of a 1.4 M

solution in Et₂O; 1.82 mmol) and the reaction mixture was

stirred for 30 min at 2338C. Copper iodide 20.173 g;

0.91 mmol) was then introduced and the reaction mixture

was vigorously stirred for 3 h at 2338C. The reaction was

quenched with water 22 ml), and the cooling bath was

removed. After dilution of the solution with 20 ml of

Et₂O, the organic layer was washed with saturated aqueous

NH₄Cl and then with water, dried over MgSO₄and concen-

trated. The crude product was puri®ed by column chromato-

graphy 2silica gel; pentane) to afford 0.203 g of 3a 281%

yield) as a colorless liquid. IR 2neat): 3072, 2926, 2852,

3.1.15. +E)-4-+Phenyltelluro)-3-nonene +3n). The same

procedure as for the preparation of 3l was duplicated,

using triethylborane and phenyltellurenyl iodide. Puri®ca-

tion was carried out by column chromatography 2silica gel

pretreated with triethylamine/pentane 25:95, v/v); eluting

with pentane). 3n was obtained as a yellow liquid in 62%

yield. IR 2neat): 3066, 2961, 2928, 2856, 1574, 1473, 1434,

1377, 1140, 1064, 1018, 731, 692 cm²¹

;

¹H NMR

2400 MHz, CDCl₃): d 0.85 23H, t, J7.3 Hz), 1.00 23H, t,

J7.5 Hz), 1.19±1.28 24H, m), 1.45 22H, m), 2.16 22H,

quint., J7.3 Hz), 2.33 22H, t, J7.5 Hz), 6.20 21H, t,

J7.3 Hz), 7.18±7.26 23H, m), 7.70 22H, m); ¹³C NMR

222.5 MHz, CDCl₃): d 14.0, 14.1, 22.5, 23.6, 29.3, 31.1,

35.8, 114.3, 119.4, 127.3, 129.1, 137.7, 146.5; MS 2EI):

332 2M¹, 73), 276 26), 208 237), 130 26), 83 234), 77 248),

69 2100), 55 276); HRMS: m/z for C₁₅H₂₂Te, Calcd:

332.0784. Found: 332.0792.

1584, 1476, 1446, 1025, 960, 898, 740, 692 cm²^{1 1}H

;

NMR 2400 MHz, CDCl₃): d 0.86 23H, t, J7.3 Hz), 1.11±

1.34 27H, m), 1.47 22H, m), 1.65±1.76 25H, m), 2.18 22H, t,

J7.5 Hz), 2.29 21H, m), 5.73 21H, d, J9.8 Hz), 7.14±7.18

21H, m), 7.24±7.30 24H, m); ¹³C NMR 222.5 MHz, CDCl₃):

d 14.0, 22.3, 25.8, 25.9, 31.1, 33.0, 38.4, 125.9, 128.7,

129.5, 131.8, 136.3, 143.6; MS 2EI): 274 2M¹, 50), 197

237), 150 2100), 135 218), 123 217), 109 227), 95 218), 79

223), 67 224), 55 221); HRMS: m/z for C₁₈H₂₆S, Calcd:

274.1755. Found: 274.1751.

3.1.16. +E)-4-+Butyltelluro)-3-octene +3o). The same

procedure as for the preparation of 3l was duplicated,

using triethylborane and butyltellurenyl iodide, except that

puri®cation was carried out by distillation under reduced

pressure 2bp 73±778C at 0.26 mm Hg). 3o was obtained as

a yellow liquid in 70% yield. IR 2neat): 2960, 2927, 2871,

3.1.19. +E)-1-Cyclohexyl-2-+butylthio)-1-heptene +3c).

The same procedure as for the preparation of 3a was dupli-

cated, using 1-heptyne and butylsulfenyl chloride, except

that activation and transmetallation were performed at

2238C. 3c was obtained as a colorless liquid in 86%

yield. IR 2neat): 2958, 2927, 2854, 1623, 1449, 893,

1

1637, 1459, 1377, 1247, 1161, 1140, 801 cm²¹; H NMR

2400 MHz, CDCl₃): d 0.92 26H, t, J7.3 Hz), 0.97 23H, t,

J7.5 Hz), 1.29±1.48 26H, m), 1.75 22H, m), 2.13 22H,

quint., J7.3 Hz), 2.32 22H, t, J7.5 Hz), 2.70 22H, t,

J7.3 Hz), 5.98 21H, t, J7.3 Hz); ¹³C NMR 222.5 MHz,

CDCl₃): d 6.3, 13.4, 14.0, 14.2, 22.1, 23.3, 25.1, 31.9, 33.8,

36.0, 115.8, 143.6; MS 2EI): 298 2M¹, 47), 241 26), 186 29),

1

734 cm²¹; H NMR 2400 MHz, CDCl₃): d 0.91 26H, m),

1.04±1.74 220H, m), 2.19 22H, t, J7.8 Hz), 2.24 21H, m)

2.61 22H, t, J7.4 Hz), 5.16 21H, d, J8.9 Hz); ¹³C NMR

222.5 MHz, CDCl₃): d 13.7, 14.0, 22.1, 22.5, 26.0, 28.9,

30.8, 31.2, 31.6, 31.9, 33.5, 37.9, 132.5, 133.0; MS 2EI):

9118

J. Gerard, L. Hevesi / Tetrahedron 57 ,2001) 9109±9121

268 2M¹, 23), 211 2100), 155 212), 143 29), 130 212), 115

212), 95 29), 81 212), 67 210), 55 212); Anal. Calcd for

C₁₇H₃₂S: C, 76.05; H, 12.01. Found: C, 76.06; H, 11.97.

3.1.23. +E)-4-Phenyl-3-octene +4b). The same procedure as

for the preparation of 4a was used, starting from 3g. 4b was

obtained as a colorless liquid in 87% yield. IR 2neat): 3059,

3024, 2962, 2932, 2873, 1600, 1493, 1460, 1378, 1073,

1

3.1.20. +E)-5-+Butylthio)-3-methyl-4-nonene +3f). The

same procedure as for the preparation of 3a was repeated,

using tri-sec-butylborane and butylsulfenyl chloride, except

that activation and transmetallation were performed at

2238C. 3f was obtained as a colorless liquid in 80%

yield. IR 2neat): 2960, 2930, 2872, 1653, 1460, 1378,

1032, 863, 763, 697 cm²¹; H NMR 290 MHz, CDCl₃): d

0.79±1.13 26H, m), 1.22±1.48 24H, m), 2.20 22H, quint.,

J7.3 Hz), 2.48 22H, t, J7.4 Hz), 5.63 21H, t,

J7.3 Hz), 7.19±7.36 25H, m); ¹³C NMR 222.5 MHz,

CDCl₃): d 14.0, 14.4, 21.8, 22.7, 29.4, 31.0, 126.3, 128.1,

130.6, 139.6, 143.5; MS 2EI): 188 2M¹, 21), 146 226), 131

2100), 118 269), 103 210), 91 231), 77 28); HRMS: m/z for

C₁₄H₂₀, Calcd: 188.1565. Found: 188.1569.

1164, 777, 745 cm²^{1 1}H NMR 290 MHz, CDCl₃): d

;

0.76±0.98 212H, m), 1.13±1.66 210H, m), 2.11±2.43 23H,

m), 2.62 22H, t, J6.9 Hz), 5.11 21H, d, J9.7 Hz); ¹³C

NMR 222.5 MHz, CDCl₃): d 11.9, 13.7, 14.0, 21.1, 22.1,

22.5, 30.4, 30.9, 31.2, 31.3, 31.7, 35.0, 133.2, 133.3; MS

2EI): 228 2M¹, 30), 213 28), 199 2100), 171 254), 143 26),

130 27), 115 28), 101 213), 81 211), 67 216), 55 214); Anal.

Calcd for C₁₄H₂₈S: C, 73.61; H, 12.35. Found: C, 72.96; H,

12.06.

3.1.24. +E)-6-Butyl-1,6-nonadiene +4c). The same pro-

cedure as for the preparation of 4a was duplicated, starting

from 3g and using 4-pentenylmagnesium bromide 20.5 M in

Et₂O). The puri®cation by column chromatography 2silica

gel; pentane) gave a mixture of 4c 285%) and 1,9-decadiene

215%). The latter was removed by Kugelrohr distillation

under reduced pressure to give essentially pure 4c 276%

yield) as a colorless liquid. IR 2neat): 3079, 2961, 2931,

3.1.21. Representative procedure for the cross-coupling

reaction of vinylchalcogenides with Grignard reagents.

Preparation of +E)-5-phenyl-5-decene +4a). In a 25 ml

two-necked ¯ask, equipped with an argon inlet and a

magnetic stirring bar, were introduced a solution of 3h

20.248 g; 1 mmol) in Et₂O 27 ml) and NiCl₂2dppe)

20.016 g; 0.03 mmol). Phenylmagnesium bromide 24.4 ml

of a 0.5 M solution in Et₂O; 2.2 mmol) was added and the

reaction mixture was stirred at room temperature for 15 h.

One milliliter of saturated aqueous NH₄Cl was then intro-

duced and, after dilution with Et₂O, the organic layer was

separated, washed with 10 ml of aqueous NaOH 21 M) and

with water, dried over MgSO₄, and concentrated. The crude

product was puri®ed by column chromatography 2silica gel;

pentane) to give 0.169 g of 4a 278% yield) as a colorless

liquid. IR 2neat): 3057, 3024, 2958, 2930, 2870, 2861, 1600,

1

2859, 1662, 1642, 1460, 1378, 991, 910 cm²¹; H NMR

2400 MHz, CDCl₃): d 0.92 23H, t, J7.1 Hz), 0.95 23H, t,

J7.4 Hz), 1.30±1.36 24H, m), 1.49 22H, quint., J7.7 Hz),

1.97±2.07 28H, m), 2.48 22H, t, J7.1 Hz), 4.96 21H, d,

J9.9 Hz), 5.02 21H, dm, J17.8 Hz), 5.12 21H, t,

J6.9 Hz), 5.84 21H, m); ¹³C NMR 222.5 MHz, CDCl₃):

d 14.0, 14.7, 21.0, 22.9, 27.6, 29.7, 30.8, 33.6, 36.3,

114.3, 126.8, 138.6, 139.1; MS 2EI): 180 2M¹, 2), 151 27),

137 210), 124 273), 109 221), 95 256), 84 299), 67 272), 55

2100); HRMS: m/z for C₁₃H₂₄, Calcd: 180.1878. Found:

180.1875.

3.1.25. 4-Butyl-3-octene +4d). The same procedure as for

the preparation of 4a was duplicated, starting from 3g and

using 2.4 equiv. of butylmagnesium bromide 20.5 M in

Et₂O). 4d was obtained as a colorless liquid in 88% yield.

IR 2neat): 2961, 2931, 2874, 2861, 1661, 1462, 1379,

;

1494, 1463, 1379, 1105, 762, 697 cm²^{1 1}H NMR

2400 MHz, CDCl₃): d 0.87 23H, t, J7.1 Hz), 0.93 23H, t,

J7.1 Hz), 1.30±1.43 28H, m), 2.19 22H, q, J7.3 Hz), 2.48

22H, t, J7.1 Hz), 5.63 21H, t, J7.3 Hz), 7.18±7.35 25H,

m); ¹³C NMR 222.5 MHz, CDCl₃): d 13.9, 14.0, 22.5, 22.7,

28.3, 29.5, 29.7, 30.9, 32.1, 126.3, 128.1, 129.1, 140.1,

143.6; MS 2EI): 216 2M¹, 24), 174 210), 159 234), 145

28), 131 222), 118 2100), 105 27), 91 243), 77 26); HRMS:

m/z for C₁₆H₂₄, Calcd: 216.1878. Found: 216.1880.

1

850 cm²¹; H NMR 290 MHz, CDCl₃): d 0.85±1.01 29H,

m), 1.21±1.48 28H, m), 1.84±2.07 26H, m), 5.09 21H, t,

J7.0 Hz); ¹³C NMR 222.5 MHz, CDCl₃): d 14.0, 14.7,

21.0, 22.6, 22.9, 29.7, 30.5, 30.8, 36.6, 126.3, 139.1; MS

2EI): 168 2M¹, 37), 126 211), 111 29), 97 29), 84 2100), 69

287), 55 275); HRMS: m/z for C₁₂H₂₄, Calcd: 168.1878.

Found: 168.1874.

3.1.22. +Z)-5-Phenyl-5-decene +4a⁰). The same procedure

as for the preparation of 4a was duplicated, starting from

2Z)-5-2phenylthio)-5-decene 3h⁰and using 8 mol% of

NiCl₂2dppe). After 20 h at room temperature, the

conversion was incomplete 250% GC; no evolution was

observed after a prolonged time of stirring). The puri®cation

by column chromatography 2silica gel; pentane) gave 4a⁰

228% yield) as a colorless liquid. IR 2neat): 3058, 3023,

2958, 2929, 2859, 1601, 1493, 1464, 1442, 1379, 1105,

3.1.26. +E)-4-Phenyl-3-nonene +4e). The same procedure as

for the preparation of 4a was duplicated, starting from 3k

and using 1.5 equiv. of phenylmagnesium bromide 20.5 M

in Et₂O). 4e was obtained as a colorless liquid in 82% yield.

IR 2neat): 3059, 3025, 2961, 2931, 2872, 2861, 1600, 1493,

1462, 1377, 863, 759, 697 cm²^{1 1}H NMR 2400 MHz,

;

CDCl₃): d 0.85 23H, t, J7.1 Hz), 1.05 23H, t, J7.5 Hz),

1.23±1.35 26H, m), 2.20 22H, quint., J7.5 Hz), 2.47 22H, t,

J7.3 Hz), 5.63 21H, t, J7.3 Hz), 7.18±7.35 25H, m); ¹³C

NMR 222.5 MHz, CDCl₃): d 14.0, 14.4, 21.9, 22.5, 28.5,

29.7, 31.8, 126.3, 128.1, 130.6, 139.7, 143.5; MS 2EI): 202

2M¹, 21), 159 26), 146 230), 131 2100), 118 284), 103 210),

91 234), 77 28); HRMS: m/z for C₁₅H₂₂, Calcd: 202.1722.

Found: 202.1717.

1

1071, 770, 702; H NMR 2400 MHz, CDCl₃): d 0.80±0.87

26H, m), 1.21±1.33 28H, m), 1.91 22H, q, J7.2 Hz),

2.31 22H, t, J6.8 Hz), 5.42 21H, t, J7.3 Hz), 7.11±7.33

25H, m); ¹³C NMR 222.5 MHz, CDCl₃): d 13.9, 14.0,

22.3, 28.6, 30.4, 32.4, 39.0, 126.2, 127.2, 127.9, 128.4,

140.9, 141.7; MS 2EI): 216 2M¹, 21), 174 211), 159 234),

145 28), 131 222), 118 299), 117 2100), 105 27), 91 243), 77

26).

The same compound could be obtained starting from 3n. In

this case, NiCl₂2PPh₃)₂25 mol%) was used as the catalyst

J. Gerard, L. Hevesi / Tetrahedron 57 ,2001) 9109±9121

9119

with THF as the solvent, and the reaction mixture was

heated to re¯ux for 3 h 277% yield).

38), 154 28), 139 26), 126 23), 112 223), 97 269), 83 279),

69 274), 55 2100); HRMS: m/z for C₁₄H₂₈, Calcd: 196.2191.

Found: 196.2189.

3.1.27. +Z)-4-Butyl-3-nonene +4f). The same procedure as

for the preparation of 4a was duplicated, starting from 3k

and using 5.0 equiv. of BuMgBr 20.5 M in Et₂O). 4f was

obtained as a colorless liquid in 73% yield. IR 2neat): 2961,

3.1.31. Representative procedure for the C±Te cleavage

of vinyltellurides with butyllithium +Path A). Prepara-

tion of +E)-2-butyl-1-phenyl-2-penten-1-ol +5a). In a

25 ml two-necked ¯ask, equipped with an argon inlet and

a magnetic stirring bar, was introduced a THF solution

23 ml) of 3o 20.244 g; 0.825 mmol). At 2788C was added

0.57 ml of n-butyllithium 21.6 M in hexane; 0.91 mmol),

and the reaction mixture was stirred for 30 min at 2788C

prior to the introduction of a THF solution 22 ml) of benzal-

dehyde 20.097 g; 0.91 mmol). The reaction mixture was

stirred for 30 min at 2788C, then the cooling bath was

removed, followed by 30 min of stirring at room tempera-

ture. Two milliliter of saturated aqueous NH₄Cl were then

added for quenching. After dilution of the solution with

20 ml of Et₂O, the organic layer was washed with saturated

aqueous NH₄Cl and with water, dried over MgSO₄and

concentrated. The crude product was puri®ed by column

chromatography 2silica gel; pentane/Et₂O: 8:2) to afford

0.132 g of 5a 273% yield) as a yellow liquid. IR 2neat):

3371, 3063, 3030, 2961, 2932, 2871, 1604, 1493, 1454,

1

2931, 2873, 2860, 1662, 1464, 1379, 851, 732 cm²¹; H

NMR 290 MHz, CDCl₃): d 0.85±1.01 29H, m), 1.26±1.50

210H, m), 1.92±2.08 26H, m), 5.09 21H, t, J7.0 Hz); ¹³C

NMR 222.5 MHz, CDCl₃): d 14.0, 14.7, 21.0, 22.5, 22.6,

28.3, 30.0, 30.5, 32.0, 36.6, 126.3, 139.1; MS 2EI): 182 2M¹,

35), 140 24), 126 28), 111 27), 97 227), 84 2100), 69 277), 55

274); HRMS: m/z for C₁₃H₂₆, Calcd: 182.2035. Found:

182.2038.

3.1.28. +E)-6-Phenyl-6-tridecene +4g). The same procedure

as for the preparation of 4a was duplicated, starting from 3l

and using 2.5 equiv. of phenylmagnesium bromide 20.5 M

in Et₂O), except that NiCl₂2PPh₃)₂24 mol%) was used as the

catalyst and the reaction mixture was heated to re¯ux for

14 h. 4g was obtained as a colorless liquid in 68% yield. IR

2neat): 3058, 3024, 2957, 2927, 2858, 1599, 1494, 1463,

1

1379, 1074, 1032, 759, 697 cm²¹; H NMR 2400 MHz,

CDCl₃): d 0.83±0.91 26H, m), 1.26±1.43 214H, m), 2.18

22H, q, J7.3 Hz), 2.47 22H, t, J7.3 Hz), 5.63 21H, t,

J7.1 Hz), 7.18±7.35 25H, m); ¹³C NMR 222.5 MHz,

CDCl₃): d 14.0, 14.1, 22.5, 22.7, 28.4, 28.6, 29.1, 29.7,

29.9, 31.8, 126.3, 128.1, 129.1, 140.1, 143.5; MS 2EI):

258 2M¹, 14), 202 26), 187 217), 159 26), 145 25), 131

221), 118 2100), 105 210), 91 241), 77 23), 55 26); HRMS:

m/z for C₁₉H₃₀, Calcd: 258.2348. Found: 258.2342.

1378, 1187, 1071, 1015, 744, 700 cm²^{1 1}H NMR

;

2400 MHz, CDCl₃): d 0.82 23H, t, J7.1 Hz), 1.01 23H, t,

J7.5 Hz), 1.13±1.27 24H, m), 1.80±1.87 22H, m), 1.95±

2.01 21H, m), 2.09 22H, quint., J7.3 Hz), 5.16 21H, s), 5.60

21H, t, J7.1 Hz), 7.24±7.37 25H, m); ¹³C NMR

222.5 MHz, CDCl₃): d 13.8, 14.3, 20.9, 23.0, 27.4, 31.7,

78.1, 126.5, 127.3, 128.1, 128.8, 140.7, 142.8; MS 2EI):

218 2M¹, 78), 189 260), 175 222), 161 2100), 143 227),

133 253), 115 217), 105 276), 91 221), 79 250), 55 220);

HRMS: m/z for C₁₅H₂₂O, Calcd: 218.1671. Found:

218.1666.

3.1.29. +Z)-6-Methyl-6-tridecene +4i). The same procedure

as for the preparation of 4a was duplicated, starting from 3l

and using 2.5 equiv. of methylmagnesium bromide 23 M in

Et₂O), except that NiCl₂2dppp) 25 mol%) was used as the

catalyst and the reaction mixture was heated to re¯ux for

8 h. 4i was obtained as a colorless liquid in 61% yield. IR

3.1.32. 1-[+E)-1-Butyl-1-butenyl]cyclohexan-1-ol +5b).

The same procedure as for the preparation of 5a was

duplicated, using cyclohexanone. The puri®cation was

carried out by column chromatography 2silica gel; pentane/

Et₂O: 9:1) to afford 5b as a yellow liquid in 70% yield. IR

2neat): 3413, 3043, 2935, 2870, 1453, 1377, 1257, 1150,

1

2neat): 2959, 2927, 2858, 1667, 1465, 1378, 724 cm²¹; H

NMR 2400 MHz, CDCl₃): d 0.87±0.92 26H, m), 1.22±1.38

214H, m), 1.67 23H, br s), 1.87±2.01 24H, m), 5.11 21H, t,

J7.0 Hz); ¹³C NMR 222.5 MHz, CDCl₃): d 14.0, 14.1,

22.7, 23.4, 27.7, 27.8, 29.1, 30.1, 31.7, 31.8, 125.3, 135.4;

MS 2EI): 196 2M¹, 28), 140 25), 125 218), 112 215), 97 224),

83 249), 69 2100), 55 267); HRMS: m/z for C₁₄H₂₈, Calcd:

196.2191. Found: 196.2194.

1

1133, 1035, 959, 857 cm²¹; H NMR 290 MHz, CDCl₃): d

0.85±1.06 26H, m), 1.20±1.68 215H, m), 1.88±2.21 24H,

m), 5.45 21H, t, J7.0 Hz); ¹³C NMR 222.5 MHz, CDCl₃):

d 13.9, 14.5, 21.2, 22.2, 23.5, 25.7, 27.5, 33.1, 36.5, 74.2,

125.7, 145.5; MS 2EI): 210 2M¹, 29), 181 291), 167 242),

153 215), 139 2100), 125 220), 111 224), 81 230), 69 242), 55

244); HRMS: m/z for C₁₄H₂₆O, Calcd: 210.1984. Found:

210.1984.

3.1.30. 5-Butyl-5-decene +4j). The same procedure as for

the preparation of 4a was duplicated, starting from 3m and

using 2.5 equiv. of butylmagnesium bromide 20.5 M in

Et₂O), except that NiCl₂2dppp) 23 mol%) was used as the

catalyst and the reaction mixture was heated to re¯ux for

14 h. The puri®cation by column chromatography 2silica

gel; pentane) gave a mixture of 4j 283%) and 2Z)-5-decene

217%). The latter was removed by Kugelrohr distillation

under reduced pressure to give essentially pure 4j 230%

yield) as a colorless liquid. IR 2neat): 2958, 2928, 2872,

3.1.33. Representative procedure for the C±Te cleavage

of vinyltellurides with dilithium butyl 2-thienyl cyano-

cuprate +Path B). Preparation of 3-[+E)-1-butyl-1-

butenyl]cyclohexanone +6a). In a 25 ml two-necked ¯ask,

equipped with an argon inlet and a magnetic stirring bar,

was introduced a THF solution 22 ml) of thiophene 20.210 g;

2.5 mmol). n-Butyllithium 21.56 ml of a 1.6 M solution in

hexane; 2.5 mmol) was added at 2788C, the temperature

was raised to 2108C, and the mixture was stirred for

30 min. This solution was transferred via cannula to another

¯ask containing a suspension of CuCN 20.180 g; 2.0 mmol)

in THF 23 ml) previously cooled to 2788C. Removing the

1

2859, 1661, 1464, 1379, 1106, 847, 730 cm²¹; H NMR

290 MHz, CDCl₃): d 0.85±0.97 29H, m), 1.27±1.38 212H,

m), 1.89±2.08 26H, m), 5.10 21H, t, J7.0 Hz); ¹³C NMR

222.5 MHz, CDCl₃): d 14.0, 22.4, 22.5, 22.9, 27.4, 29.8,

30.6, 30.8, 32.4, 36.7, 124.6, 139.5; MS 2EI): 196 2M¹,

9120

J. Gerard, L. Hevesi / Tetrahedron 57 ,2001) 9109±9121

cooling bath gave an homogeneous pale yellow solution,

which was cooled again to 2788C prior to the introduction

of n-butyllithium 21.25 ml of a 1.6 M solution in hexane;

2.0 mmol). The reaction mixture was stirred for 15 min at

2788C, and then the cooling bath was removed before the

introduction of a THF solution 23 ml) of 3o 20.592 g;

2.0 mmol). After 1 h of stirring at room temperature, the

solution was cooled to 2788C and cyclohexenone

20.195 ml; 2.0 mmol) was added. The cooling bath was

removed, and the reaction mixture was stirred for 20 min

at room temperature. A mixture of saturated aqueous

solution of NH₄Cl and NH₄OH 24:1, v/v; 10 ml) and

30 ml of ethyl acetate were then added. The organic layer

was separated, washed with brine, dried over MgSO₄and

concentrated. The crude product was puri®ed by column

chromatography 2silica gel; pentane/ethyl acetate: 96:4) to

give 0.262 g of 6a 263% yield) as a pale yellow liquid. IR

2neat): 2959, 2933, 2871, 1714, 1459, 1422, 1346, 1317,

47.2, 110.1, 128.9, 137.0, 147.6, 213.9; MS 2EI): 262

2M¹, 30), 247 24), 233 29), 219 212), 204 222), 191 215),

177 28), 165 228), 153 2100), 135 224), 123 226), 109 250), 97

290), 81 261), 69 264), 55 268); HRMS: m/z for C₁₈H₃₀O,

Calcd: 262.2297. Found: 262.2297.

References

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Functional Group Transformations; Ley, S. V., Ed.;

Pergamon: New York, 1995; Vol. 2, p. 951.

È

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1

1260, 1222, 1104, 1030, 930, 873, 753 cm²¹; H NMR

È

4. Binger, P.; Koster, R. Synthesis 1973, 309. 2b) Corey, E. J.;

2400 MHz, CDCl₃): d 0.92 23H, t, J6.9 Hz), 0.97 23H, t,

J7.3 Hz), 1.29±1.35 24H, m), 1.54±1.67 22H, m), 1.91

21H, m), 1.94±2.12 25H, m), 2.25±2.42 25H, m), 5.15

21H, t, J6.8 Hz); ¹³C NMR 222.5 MHz, CDCl₃): d 13.9,

14.5, 20.9, 22.9, 23.0, 25.4, 29.4, 31.0, 31.6, 41.3, 45.1,

47.7, 126.4, 141.3, 212.0; MS 2EI): 208 2M¹, 82), 179

248), 165 2100), 151 272), 137 230), 123 249), 109 234), 95

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3.1.34. +E)-5-Butyl-5-octen-2-one +6b). The same pro-

cedure as for the preparation of 6a was duplicated, using

methyl vinyl ketone. 6b was obtained as a pale yellow liquid

in 59% yield. IR 2neat): 2960, 2932, 2873, 2861, 1719,

6. Hooz, J.; Mortimer, R. Can. J. Chem. 1978, 56, 2786.

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1665, 1460, 1360, 1284, 1160, 1070, 940, 837, 759 cm²¹

;

¹H NMR 2400 MHz, CDCl₃): d 0.93 23H, t, J7.3 Hz), 0.96

23H, t, J7.7 Hz), 1.31±1.37 24H, m), 1.98±2.06 24H, m),

2.18 23H, s), 2.27 22H, t, J7.5 Hz), 2.55 22H, t, J7.8 Hz),

5.12 21H, t, J7.1 Hz); ¹³C NMR 222.5 MHz, CDCl₃): d

14.0, 14.5, 20.9, 22.7, 29.9, 30.7, 42.6, 127.0, 137.3,

208.9; MS 2EI): 182 2M¹, 2), 164 217), 153 24), 139 26),

124 217), 109 212), 95 240), 82 2100), 67 229), 55 237);

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182.1676.

9. Pelter, A.; Colclough, M. E. Tetrahedron Lett. 1986, 27, 1935.

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3.1.35. +3R,5R)-5-[+E)-1-Butyl-1-butenyl]-1-methyl-4-+1-

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carvone. The puri®cation was carried out by column chro-

matography 2silica gel; pentane/ethyl acetate: 98:2) to afford

12. Pelter, A.; Subrahmanyam, C.; Laub, R. J.; Gould, K. J.;

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1

6c as a colorless liquid in 65% yield. While H and ¹³C

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1

1231, 1210, 1176, 891, 657 cm²¹; H NMR 2400 MHz,

CDCl₃): d 0.90 23H, t, J6.8 Hz), 0.93 23H, t, J7.3 Hz),

1.04 23H, d, J6.8 Hz), 1.24±1.36 24H, m), 1.72 23H, s),

1.74±1.80 22H, m), 1.93 21H, dm, J13.7 Hz), 2.01 22H,

quint., J7.3 Hz), 2.06±2.12 21H, m), 2.27 21H, ddd,

J14.7, 11.2 and 1.5 Hz), 2.49±2.57 22H, m), 2.65 21H,

m), 2.76 21H, m), 4.72 21H, s), 4.78 21H, s), 4.81 21H, t,

J7.1 Hz); ¹³C NMR 222.5 MHz, CDCl₃): d 12.0, 14.0,

14.6, 21.0, 21.2, 22.8, 30.9, 31.1, 32.9, 39.8, 45.3, 45.4,

J. Gerard, L. Hevesi / Tetrahedron 57 ,2001) 9109±9121

9121

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Article Doi

Chalcogen electrophile induced rearrangement of 1-alkynyltrialkyl borates: Controlled syntheses of trisubstituted olefins from 1-alkynes

DOI: 10.1016/S0040-4020(01)00904-8

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Full text of DOI:10.1016/S0040-4020(01)00904-8

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