Palladium-catalyzed phosphination of functionalized aryl triflates

Article abstract of DOI:10.1016/j.tet.2003.10.061

Catalytic user-friendly approach to the syntheses of various functionalized aromatic phosphines from their corresponding substituted aryl triflates and triarylphosphines was accomplished. This method is carried out in neutral media and compatible with man

Full text of DOI:10.1016/j.tet.2003.10.061

Tetrahedron 59 (2003) 10295–10305
Palladium-catalyzed phosphination of functionalized aryl triflates
*
Fuk Yee Kwong, Chi Wai Lai, Michael Yu, Yuan Tian and Kin Shing Chan
Open Laboratory of Chirotechnology of the Institute of Molecular Technology for Drug Discovery and Synthesis,† Department of Chemistry,
The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, China
Received 16 June 2003; revised 18 September 2003; accepted 12 October 2003
Abstract—Catalytic user-friendly approach to the syntheses of various functionalized aromatic phosphines from their corresponding
substituted aryl triflates and triarylphosphines was accomplished. This method is carried out in neutral media and compatible with many
functional groups including aldehyde, keto, ester, nitrile, ether and pyridyl groups.
q 2003 Elsevier Ltd. All rights reserved.
1. Introduction
Functionalized aromatic phosphines are an important type
of ligands in transition metal-catalyzed reactions.1,2 How-
ever, the synthesis of substituted tertiary phosphines by
Grignard/organolithium reagents is limited to aryl
bromides/iodides and is not applicable to triflate substrates.3
As phenols and their derivatives are easily accessible, it is
valuable to develop a transition metal-catalyzed phosphina-
tion of functionalized aryl triflates. Several palladium- and
nickel-catalyzed phosphination of aryl sulfonates have been
reported (Scheme 1). The Pd/Ph2P(O)H protocol for
phosphinylation of aryl triflates using diphenylphosphine
oxide as the phosphinylating agent was found to be
compatible with some functional groups such as ester and
ether groups (Scheme 1).4 Nevertheless, this reaction could
not be applied to the synthesis of BINAPO since only one
triflate moiety (from BINOL ditriflates) was found to
undergo phosphinylation as reported by Morgan et al.5
Moreover, Bringmann, also demonstrated the failed
transformation of 2,6-disubstituted aryl triflates to diphenyl-
phosphine oxide group by palladium-catalyzed phosphinyl-
ation.6 Using the above phosphinylation, the desired
aromatic phosphine products usually were accomplished
with a subsequent reduction of phosphine oxide inter-
mediate with trichlorosilane, which is a disadvantage of this
methodology. Recently, Lipshutz and co-workers reported
palladium-mediated couplings of aryl nonaflates and
triflates with diphenylphosphine–borane (Ph2PH–BH3) in
the preparation of broane-stabilized unsymmetrical aryl-
phosphines (Scheme 1).7 The diphenylphosphine–borane is
Scheme 1. Transition metal-catalyzed phosphination of aryl triflates.
an air-stable reagent and readily prepared from com-
Keywords: phosphination; aryl triflates; triphenylphosphine.
*
mercially available Ph2PCl and BH3–THF in the presence
Corresponding author. Tel.: þ852-2609-6376; fax: þ852-2603-5057;
of lithium aluminum hydride.8 This method offers a low
temperature advantage, but is sensitive to amine and
pyridine groups, and further deprotection of borane group
e-mail: ksc@cuhk.edu.hk
A University Grants Committee, Area of Excellence Scheme (Hong
Kong).
†
0040–4020/$ - see front matter q 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2003.10.061

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F. Y. Kwong et al. / Tetrahedron 59 (2003) 10295–10305
is required by using diethylamine to yield free phosphines.9
The use of Ph2PH protocol catalyzed by palladium
complexes was applicable to aryl triflates (thyrosine and
glycine derivatives) in DMSO solvent (Scheme 1).10
Apart from the palladium complexes, nickel catalysts were
used in the transition metal-catalyzed phosphination. Cai
et al. reported the first example of NiCl2(dppe) catalyzed
phosphination of BINOL ditriflate using diphenylphosphine
(Ph2PH) in the synthesis of BINAP (Scheme 1).11 This
direct nickel-catalyzed phosphination was found to be
effective in the synthesis of diphosphines from ditriflates
which failed in the Pd/Ph2P(O)H methodology previously.5
Most importantly, these reaction conditions were amenable
to the synthesis of optically active BINAPs from their
optically active BINOL ditriflates. The minor drawbacks of
this reaction are the use of air- and moisture-sensitive
diphenylphosphine reagents and the requirement of portion-
wise addition of Ar2PH during the course of reaction.
Recently, Ager and co-workers had used chlorodiphenyl-
phosphine (Ph2PCl) instead of diphenylphosphine as the
phosphinating reagent (Scheme 1).12 Zinc performs two
functions in the Ni/Ph2PCl/Zn protocol; it reduces Ni(II) to
Ni(0) and presumably gives rise to zinc phosphide Ph2-
PZnCl which reacts with aryl triflates (Scheme 1). Although
air-sensitive reagent is required, this method is mild.
Synthesis of optically active BINAP without racemization
is accomplished.12
Figure 1. Effect of triphenylphosphine on the phosphination of aryl triflate.
2.3 equiv. of Ph3P in DMF at 110–1158C under a nitrogen
atmosphere. These reaction conditions were then applied to
the syntheses of other functionalized aryl phosphines.
4-Formylphenyl triflate was directly phosphinated by
triphenylphosphine to form 4-(diphenylphosphino)benzal-
dehyde (Table 1, entry 2). In contrast, the previous
preparation of this phosphine, which finds many appli-
cations in water-soluble polymers16 and porphyrins,17
involved a muti-step synthesis requiring protection/depro-
tection of the aldehyde group.18 Other functional groups,
such as ester, nitrile, keto, ether and chloride were tolerated
with this phosphination reaction (Table 1, entries 2–7).
However, previous syntheses of ester and nitrile containing
phosphines required a long synthetic pathway.19 A sterically
hindered substrate, 2-methoxyphenyl triflate successfully
reacted with Ph3P to give 2-(diphenylphosphino)anisole
(Table 1, entry 8). In contrast, the analogous less reactive
2-bromoanisole did not react. The transformation of
quinolyl and pyridyl triflates to their corresponding
phosphines required much longer reaction times (Table 1,
entries 10–11). Presumably the chelating heteroatom
coordinated to the palladium center rendered the complex
coordinatively saturated.20 Hence the catalytic activity was
reduced. The quinolyl phosphine (entry 11) is a useful
bidentate P,N ligand.21
We have recently described that triarylphosphines could be
used as the diarylphosphinating agents for the preparation of
substituted phosphines from the corresponding aryl
bromides.13 As phenols and their sulfonate derivatives are
easily accessible, herein we report an alternative user-
friendly and operationally simple palladium-catalyzed
phosphination of functionalized aryl triflates using air-stable
and economical triarylphosphines as the diarylphosphinat-
ing agents (Eq. (1)).14
ð1Þ
2. Results and discussions
Although this palladium-catalyzed phosphination tolerated
many functional groups, it was incompatible with nitro
group (Table 1, entry 12) which was reduced. The
preparation of diphosphines from ditriflates was unsuccess-
ful (Table 1, entry 13). Presumably, the inhibition is due to
the inhibiting effect of excess phosphine (Table 1, entry 13
and Fig. 1). Extremely sterically hindered MOP precursor
was found to be inferior in the reaction conditions (Table 1,
entry 14). No significant electronic effects were observed in
these phosphination reactions.
4-Acetylphenyltriflate (1) was used as the prototypical
substrate for screening optimal reaction conditions. Both
Pd(PPh3)4 and Pd(OAc)2 were found to be effective
catalysts.15 Pd(OAc)2 was preferred since other triaryl-
phosphines can be used as the phosphinating agents.15 Polar
aprotic solvents were found to be effective and DMF was the
solvent of choice.15 The amount of triphenylphosphine
agent added was found to be crucial in the phosphination of
aryl triflates. The optimal amount of triphenylphosphine
used was found to be about 2.3–2.5 equiv. (Fig. 1).
Other triarylphoshphines were found to be effective
diarylphosphinating agents for palladium catalyzed phos-
phination of aryl triflates (Table 2). The 4-acetophenyl
Thus, the optimal reaction conditions for the transformation
of 4-acetylphenyltriflate (1) to 4-(diphenylphosphino)aceto-
phenone (2) were found to require 10 mol% Pd(OAc)2 and

F. Y. Kwong et al. / Tetrahedron 59 (2003) 10295–10305
Table 1. Palladium-catalyzed phosphination of aryl triflatesa
10297
Entry
Substrates
Products
Time (h)
2
Percentage yieldb
37
1
2
3
3
3
31
38
4
5
6
7
5
5
6
6
30
45c
50c
20 (25)c
8
8
28
9
4
51c
10
24
20 (33)c
11
72
45
12
13
48
96
Nild
Nild
14
120
Nile
a
Reaction conditions: ArOTf (0.5 mmol), Pd(OAc)2 (0.05 mmol), PPh3 (1.15 mmol) and dry DMF (2 mL) were heated to 110–1158C under nitrogen.
Isolated yields were reported.
GC yields were reported.
Starting material was consumed within 24 h.
Starting material remained.
b
c
d
e
triflate was diarylphosphinated by tri(m-xylyl)phosphine,
Ar2PhP in the reaction of Ph3P with ArOTf. Other side
reactions such as reduction of ArOTf or unfavorable
equilibrium (see mechanistic discussion) may account for
the low yield.
tri(p-methoxyphenyl)phosphine and tri(p-tolyl)phosphine to
yield the corresponding aromatic phosphines in moderate
yields with similar reaction rates (Table 2, entries 1–3).
Sterically hindered tri(o-tolyl)phosphine did not react at all
(Table 2, entry 4). Therefore, an array of tailor-made
phosphines can be prepared easily through this direct
methodology.
A user-friendly and environmentally benign phosphination
was successfully carried out in solvent-free conditions
(Table 3).22 No significant electronic effect was observed in
the solvent-free phosphination since both electron-with-
drawing and -donating substrates exhibited similar reaction
rates (Table 3). Aryl nonaflate was found to be effective in
this reaction (Table 3, entry 5). ortho-Substituted aryl
The yields of the phosphination remained low despite the
operational simplicity. All aryl triflates were consumed
completely. We did not observe the formation of any

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F. Y. Kwong et al. / Tetrahedron 59 (2003) 10295–10305
Table 2. Palladium-catalyzed phosphination of 4-acetophenyl triflate with triarylphosphines
ð3Þ
Entry
1
PAf3
Products
Time (h)
Percentage yielda
8
28
2
3
6
8
24
30
4
72
No rxnb
a
Isolated yields were reported.
Starting material remained.
b
Table 3. Palladium-catalyzed phosphination under solvent-free conditions
ð4Þ
Entry
1
Substrate
Product
Time (d)
1.0
Percentage yielda
38
2
3
1.0
2.5
40
42
4
1.5
42
5
6
1.5
0.8
43
26
7
8
1.5
2.5
3.5
38
37
27
9
a
Isolated yields were reported.

F. Y. Kwong et al. / Tetrahedron 59 (2003) 10295–10305
10299
triflates reacted in solvent-free conditions to give the desired
phosphine products (Table 3, entries 8–9). In contrast, the
corresponding ortho-substituted aryl bromides did not react
in these reaction conditions. The rates of the reactions in
solvent-free conditions were slower than that in DMF.
Presumably, the high viscosity of the reaction mixture was
responsible. As Ph3P melted at 798C, at the reaction
temperature of 1108C, triphenylphosphine behaved as the
solvent, ligands and phosphinating agents.
The selectivity of the phosphination can be observed when
naphthyldiphenylphosphine was used as the phosphinating
agent (Scheme 2). A 19:1 ratio of compounds 2–40 was
obtained for 4-acetophenyl triflate substrate (Scheme 2,
Eq. (5)). On the other hand, when a sterically more hindered
8-quinolyl triflate was used, the selectivity decreased to the
ratio of 4:1 (22–41) (Scheme 2, Eq. (6)). Selective Caryl
–
P.Calkyl–P activation was observed when diphenylmethyl-
phosphine was used as the phosphinating agent for quinolyl
triflate (Scheme 2, Eq. (6)). The ease of Caryl–P bond
cleavage was possibly due to the preferred oxidative
addition of less hindered Caryl–P bond over the Calkyl–P
bond.23 Moreover, the formation of a more stable Pd-aryl
than Pd-alkyl intermediate was also a factor. Therefore, only
8-(methylphenyl)phosphino-quinoline (42) product was
detected from GC-MS. The lower yield of the product was
likely due to its air-sensitivity during purification.
Scheme 3. Suggested mechanism for palladium-catalyzed phosphination.
situ reduced by triphenylphosphine to form complex A,
PdL2 (L¼triphenylphosphine).26,27 This active palladium
complex A then undergoes oxidative addition with
functionalized aryl triflates to afford palladium complex B
(Scheme 3).28 The complex C subsequently undergoes
reductive elimination with triphenylphosphine to produce a
phosphonium salt D and palladium complex A. Such
Pd-catalyzed phosphonium salt formation for meta- and
para- but not ortho-substituted aryl bromides has been
Scheme 2. Selectivities in palladium-catalyzed phosphination of aryl
triflates.
The promoting effect of iodide24 in transition metal-
catalyzed reaction was not observed in this phosphination.
Upon the addition of NaI, the rate and yield of phosphina-
tion were lowered (Eq. (8)). No 4-iodoacetophenone was
detected by GC-MS analysis during the course of the
reaction. The suppressing effect was likely caused by the
reduction in the rate of added iodide in the Pd-aryl/P-aryl
exchange through the formation of Pd-iodide complex,25
which is very likely the rate determining step in the
catalysis.
Scheme 3 illustrates a plausible mechanism for the reaction
involving Pd(0)/Pd(II) cycles. Palladium(II) acetate is in
Figure 2. GC time profile for palladium-catalyzed phosphination.

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F. Y. Kwong et al. / Tetrahedron 59 (2003) 10295–10305
reported.29 The GC time profile for palladium-catalyzed
phosphination showed that, the consumption of aryl triflate
11 occurred at the first 2 h of the reaction without any
phosphine product 12 formed (Fig. 2). These data likely
supported the rapid formation of phosphonium salt
intermediate before the formation of product (Fig. 2).
(30 m£0.25 mm). The GC yields of the products were
estimated using authentic samples together with anthracene
as the internal standard.
3.2. General procedure for preparation of aryl triflates
4-Nitrophenol (0.5 g, 3.6 mmol) was dissolved in dry
dichloromethane (20 mL) under nitrogen at room tempera-
ture followed by the addition of dry pyridine (0.87 mL,
10.8 mmol). Trifluoromethanesulfonic anhydride (triflic
anhydride) (0.67 mL, 4.0 mmol) in dry dichloromethane
(10 mL) was then added dropwise. The color of the solution
was changed from yellow to orange with white fume
evolved. The reaction mixture was allowed to stir at room
temperature for an hour. Water (20 mL) was then added and
the reaction mixture was extracted with dichloromethane
(3£15 mL). The combined organic phase was washed with
diluted hydrochloric acid, water, brine and dried over
MgSO4. The residue after rotary evaporation was purified
by column chromatography on silica gel using a solvent
mixture (hexane/ethyl acetate¼3:1) as the eluent to obtain
the 4-nitrophenyltrifluoromethanesulfonate (878 mg, 90%)
as a pale yellow solid. Rf¼0.7 (hexane/ethyl acetate¼3:1);
mp 52–548C (lit.46 52–558C); 1H NMR (300 MHz, CDCl3)
d 7.47 (dd, 2 H, J¼1.4, 7.8 Hz), 8.37 (dd, 2H, J¼1.4,
7.9 Hz); MS (EI): m/z (relative intensity) 271 (Mþ, 100),
255 (17), 225 (40), 138 (67).
The palladium complex A then undergoes oxidative
addition by carbon–phosphorus bond cleavage of the
phosphonium salt D to generate the coordinated ArPPh2
Pd-complex (Scheme 3).30,31 Finally, ligand substitution by
triphenylphosphine to Pd(II) complex E gives ArPPh2 and
Pd–phenyl complex G. The PdL2 species is regenerated by
reductive elimination of triphenylphosphine and Pd bound
phenyl group to yield the tetraphenylphosphonium triflate
co-product (Scheme 3). Although the tetraphenylphos-
phonium salt was not isolated, it was detected by 31P
NMR (d¼24.0 ppm)32 in the crude reaction mixture.
Therefore, 2 equiv. of PPh3 were required. The first one
serves as the diphenylphosphinating agent and the second
one yields the phosphonium salt co-product.
In conclusion, a catalytic user-friendly phosphination using
triarylphosphines as the phosphinating reagents was
developed and optimized. This carbon–phosphorus bond
formation was compatible with a number of functional
groups, including aldehyde, keto, ester, nitrile, ether,
pyridine and etc. This phosphination employed air-stable
triphenylphosphine as the phosphinating reagent, and the
reaction was also carried out in neutral media. This process
has a great potential to access a variety of substituted
phosphines from the reaction of triarylphopshines with
various functionalized aryl triflates.
3.3. General procedure for palladium-catalyzed
phosphination (methods A) and solvent-free palladium-
catalyzed phosphination (methods B)
Method A. 4-Cyanophenyltrifluoromethanesulfonate
(251 mg, 1.0 mmol), palladium(II) acetate (22.4 mg,
0.1 mmol), triphenylphosphine (603 mg, 2.3 mmol) were
dissolved in DMF (2 mL) in a Teflon screw-capped flask
under nitrogen. The reaction mixture was heated to 110–
1158C for 2 h and the color of the solution was changed
from pale yellow to red. 4-(Diphenylphosphino)benzonitrile
was obtained (108 mg, 38%) as a white solid after purified
by column chromatography on silica gel.
3. Experimental
3.1. General considerations
Unless otherwise noted, all reagents were purchased from
commercial suppliers and used without purification.
Dichloromethane and pyridine were distilled from
anhydrous calcium chloride under nitrogen. N,N-Dimethyl-
formamide was distilled from magnesium sulfate under
reduced pressure.33 Thin layer chromatography was per-
formed on Merck precoated silica gel 60 F254 plates. Silica
gel (Merck, 70–230 and 230–400 mesh) was used for
column chromatography. 1H NMR spectra were recorded on
a Bruker DPX 300 (300 MHz) spectrometer. Spectra were
referenced internally to the residual proton resonance in
CDCl3 (d 7.26 ppm), or with tetramethylsilane (TMS, d
0.00 ppm) as the internal standard. Chemical shifts (d) were
reported as part per million (ppm) in d scale downfield from
TMS. 13C NMR spectra were recorded on a Bruker DPX
300 (75 MHz) spectrometer and referenced to CDCl3 (d
77.00 ppm). 31P NMR spectra were recorded on a Varian
400 (162 MHz) and referenced to 85% H3PO4 externally.
Coupling constants (J) were reported in Hertz (Hz). Mass
spectra (EIMS and FABMS) were recorded on a HP 5989B
Mass Spectrometer. High resolution mass spectra (HRMS)
were obtained on a Bruker APEX 47e FT-ICR mass
spectrometer (ESIMS). GC-MS analyses were conducted
on a HP G1800C GCD system using a HP5MS column
Method B. 4-Cyanophenyltrifluoromethanesulfonate
(126 mg, 0.5 mmol), palladium(II) acetate (11.2 mg,
0.05 mmol) and triphenylphosphine (301 mg, 1.15 mmol)
were mixed in a Teflon screw-capped flask under nitrogen.
The reaction mixture was heated to 110–1158C to yield
4-(diphenylphosphino)benzonitrile (55 mg, 38%) as a white
solid.
3.3.1. 4-Acetylphenyltrifluoromethanesulfonate (1).34
The general procedure for synthesis of aryl triflate was
used. 4-Hydroxyacetophenone (2.7 g, 20.0 mmol), pyridine
(4.8 mL, 40.0 mmol), triflic anhydride (3.7 mL, 22.0 mmol)
and dry CH2Cl2 were used to yield 4-acetylphenyltrifluoro-
methanesulfonate (1) (4.6 g, 87%) as a colorless liquid.
1
Rf¼0.41 (hexane/ethyl acetate¼5:1); H NMR (300 MHz,
CDCl3) d 2.65 (s, 3H), 7.43 (d, 2H, J¼8.7 Hz), 8.00 (d, 2H,
J¼8.4 Hz); MS (EI): m/z (relative intensity) 268 (Mþ, 48),
189 (100), 161 (42).
3.3.2. 4-(Diphenylphosphino)acetophenone (2).35
Method A. 4-Acetylphenyltriflate (1) (134 mg, 0.5 mmol),

F. Y. Kwong et al. / Tetrahedron 59 (2003) 10295–10305
10301
palladium(II) acetate (11.2 mg, 0.05 mmol), triphenyl-
phosphine (301 mg, 1.15 mmol) and DMF (2 mL) were
used to yield 4-(diphenylphosphino)acetophenone (2)
(56 mg, 37%) as a white solid. Rf¼0.3 (hexane/ethyl
NMR (300 MHz, CDCl3) d 7.28–7.39 (m, 12H), 7.57 (dd,
2 H, J¼1.2, 8.4 Hz); 13C NMR (75 MHz, CDCl3) d 111.8,
118.9, 128.8 (d, JCP¼7.4 Hz), 129.5, 131.7 (d, JCP¼5.9 Hz),
133.4 (d, JCP¼18.4 Hz), 134.0 (d, JCP¼20.2 Hz), 135.3 (d,
JCP¼10.3 Hz), 145.1 (d, JCP¼16.5 Hz); MS (EI): m/z
(relative intensity) 287 (Mþ, 100), 208 (55), 195 (8), 183
(62), 177 (12).
1
acetate¼15:1); mp 115–1188C (lit. 115–1168C); H NMR
(300 MHz, CDCl3) d 2.57 (s, 3H), 7.29–7.38 (m, 12H), 7.88
(dd, 2H, J¼1.3, 8.3 Hz); 13C NMR (75 MHz, CDCl3) d
26.6, 127.9 (d, JCP¼6.2 Hz), 128.6 (d, JCP¼7.2 Hz), 129.1,
133.2 (d, JCP¼18.5 Hz), 133.9 (d, JCP¼19.9 Hz), 135.9 (d,
JCP¼10.4 Hz), 136.7, 144.3 (d, JCP¼14.2 Hz), 197.8; MS
(EI): m/z(relative intensity) 304 (Mþ, 100), 289 (10), 261
(12), 227 (11), 183 (90), 152 (30).
3.3.7. Methyl 4-trifluoromethanesulfonyloxybenzoate
(7).34 The general procedure for synthesis of aryl triflate
was used. Methyl 4-hydroxybenzoate (913 mg, 6 mmol),
pyridine (1.5 mL, 18.0 mmol), triflic anhydride (1.1 mL,
6.6 mmol) and dry CH2Cl2 (20 mL) were used to yield
methyl 4-trifluoromethanesulfonyloxybenzoate (7) (1.6 g,
3.3.3. 4-Trifluoromethanesulfonyloxybenzaldehyde
(3).34 The general procedure for synthesis of aryl triflate
was used. 4-Hydroxybenzaldehyde (732 mg, 6.0 mmol),
pyridine (1.5 mL, 18.0 mmol), triflic anhydride (1.1 mL,
6.6 mmol) and dry CH2Cl2 (15 mL) were used to yield
4-trifluoromethane-sulfonyloxybenzaldehyde (3) (944 mg,
91%) as
a
colorless liquid. Rf¼0.52 (hexane/ethyl
1
acetate¼5:1); H NMR (300 MHz, CDCl3) d 3.92 (s, 3H),
7.34 (dt, 2H, J¼2.4, 9.0 Hz), 8.13 (dt, 2H, J¼2.3, 9.0 Hz);
MS (EI): m/z (relative intensity) 284 (Mþ, 46), 253 (77), 189
(100), 161 (17).
85%) as
a
colorless liquid. Rf¼0.5 (hexane/ethyl
1
acetate¼4:1); H NMR (300 MHz, CDCl3) d 7.44 (d, 2H,
J¼8.7 Hz), 7.99 (d, 2H, J¼8.4 Hz), 10.03 (s, 1H); MS (EI):
m/z (relative intensity) 254 (Mþ, 80), 189 (100), 161 (12).
3.3.8. Methyl 4-(diphenylphosphino)benzoate (8).38
Methyl
4-trifluoromethane-sulfonyloxybenzoate
(7)
(142 mg, 0.5 mmol), palladium(II) acetate (11.2 mg,
0.05 mmol), triphenylphosphine (301 mg, 1.15 mmol) and
dry DMF (2 mL) were used to yield methyl 4-(diphenyl-
phosphino)benzoate (8) (47 mg, 30%) as a white solid after
purified by column chromatography on silica gel using a
solvent mixture (hexane/ethyl acetate¼10:1) as the eluent.
Rf¼0.6 (hexane/ethyl acetate¼10:1); mp 105–1078C (lit.
105–1078C); 1H NMR (300 MHz, CDCl3) d 7.28–7.38 (m,
12H), 7.97 (dd, 2H, J¼1.5, 8.4 Hz); 13C NMR (75 MHz,
CDCl3) d 52.2, 128.7 (d, JCP¼7.1 Hz), 129.1, 129.3 (d,
JCP¼6.4 Hz), 133.0, 133.1 (d, JCP¼18.5 Hz), 133.9 (d,
3.3.4. 4-(Diphenylphosphino)benzaldehyde (4).36
Method A. 4-Trifluoromethane-sulfonyloxybenzaldehyde
(3) (127 mg, 0.5 mmol), palladium(II) acetate (11.2 mg,
0.05 mmol), triphenylphosphine (301 mg, 1.15 mmol) and
dry DMF (2 mL) were used to yield the 4-(diphenyl-
phosphino)benzaldehyde (4) (45 mg, 31%) as a white solid.
Rf¼0.6 (hexane/ethyl acetate¼10:1); mp¼109–1118C (lit.
109–1128C); 1H NMR (300 MHz, CDCl3) d 7.32–7.43 (m,
12H), 7.80 (dd, 2H, J¼1.5, 8.1 Hz), 10.00 (s, 1H); 13C NMR
(75 MHz, CDCl3) d 128.8 (d, JCP¼7.2 Hz), 129.3, 133.5 (d,
JCP¼18.3 Hz), 134.0 (d, JCP¼20.0 Hz), 135.7 (d,
JCP¼10.4 Hz), 136.0, 146.5 (d, JCP¼15.5 Hz), 191.9; 31P
(162 MHz, CDCl3) d 23.41; MS (EI): m/z (relative
intensity) 290 (Mþ, 100), 261 (8), 211 (9), 183 (95), 165
(12), 152 (20).
JCP¼19.9 Hz), 136.1 (d, JCP¼10.5 Hz), 144.0 (d, JCP
¼
14.0 Hz), 166.9; MS (EI): m/z (relative intensity) 320 (Mþ,
100), 289 (8), 261 (7), 207 (9), 183 (70), 166 (12).
3.3.9. 4-Chlorophenyltrifluoromethanesulfonate (9).39
The general procedure for synthesis of aryl triflate was
used. 4-Chlorophenol (0.64 g, 5.0 mmol), pyridine (1.2 mL,
15.0 mmol), triflic anhydride (0.87 mL, 5.2 mmol) and dry
CH2Cl2 (20 mL) were used to yield 4-chlorophenyltrifluoro-
methanesulfonate (9) (1.21, 93%) as a colorless oil. Rf¼0.3
(hexane); 1H NMR (300 MHz, CDCl3) d 7.28 (dd, 2H,
J¼8.7, 12.0 Hz), 7.64 (dd, 2H, J¼8.6, 12.0 Hz); MS (EI):
m/z (relative intensity) 262 (Mþ, 80), 260 (27), 225 (33),
127 (66).
3.3.5. 4-Cyanophenyltrifluoromethanesulfonate (5).34
The general procedure for synthesis of aryl triflate was
used. 4-Cyanophenol (0.71 g, 6.0 mmol), pyridine (1.5 mL,
18.0 mmol), triflic anhydride (1.1 mL, 6.6 mmol) and dry
dichloromethane (20 mL) were used to afford 4-cyano-
phenyl-trifluoromethanesulfonate (5) (1.4 g, 96%) as a
1
colorless oil. Rf¼0.6 (hexane/ethyl acetate¼3:1); H NMR
(300 MHz, CDCl3) d 7.45 (dd, 2H, J¼8.7, 12.0 Hz), 7.12
(dd, 2H, J¼8.6, 12.0 Hz); MS (EI): m/z (relative intensity)
251 (Mþ, 44), 211 (100), 173 (28).
3.3.10. 1-(Diphenylphosphino)-4-chlorobenzene (10).40
4-Chlorophenyltrifluoromethane-sulfonate (9) (130 mg,
0.5 mmol), palladium(II) acetate (11.2 mg, 0.05 mmol),
triphenylphosphine (301 mg, 1.15 mmol), anthracene
(internal standard) (89 mg, 0.5 mmol), and DMF (2 mL)
were used to yield the 1-(diphenylphosphino)-4-chloro-
benzene (10) (45% GC yield), and the yield was determined
by GC with respected to the calibration curve of the
authentic sample and anthracene.
3.3.6. 4-(Diphenylphosphino)benzonitrile (6).37 Method A.
4-Cyanophenyltrifluoro-methanesulfonate (5) (251 mg,
1.0 mmol), palladium(II) acetate (22.4 mg, 0.1 mmol),
triphenylphosphine (603 mg, 2.3 mmol) were dissolved in
DMF (2 mL) in a Teflon screw-capped flask under nitrogen.
The reaction mixture was heated to 110–1158C for 2 h and
the color of the solution was changed from pale yellow to
red. 4-(Diphenylphosphino)benzonitrile (6) was obtained
(108 mg, 38%) as a white solid after purified by column
chromatography on silica gel using a solvent mixture
(hexane/ethyl acetate¼10:1) as the eluent. Rf¼0.6 (hexane/
3.3.11. 4-tert-Butylphenyltrifluoromethanesulfonate
(11).41 The general procedure for synthesis of aryl
triflate was used. 4-tert-Butylphenol (0.75 g, 5.0 mmol),
pyridine (1.2 mL, 15.0 mmol), triflic anhydride (0.87 mL,
5.2 mmol) and dry CH2Cl2 (20 mL) were used to yield
1
ethyl acetate¼10:1); mp 120–1228C (lit. 120–1228C); H

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F. Y. Kwong et al. / Tetrahedron 59 (2003) 10295–10305
4-tert-butylphenyltrifluoromethanesulfonate (11) (1.3 g,
90%) as a colorless oil. Rf¼0.5 (hexane); 1H NMR
(300 MHz, CDCl3) d 1.33 (s, 9H), 7.18 (dd, 2H, J¼8.7,
12.1 Hz), 7.44 (dd, 2H, J¼8.6, 12.0 Hz); MS (EI): m/z
(relative intensity) 282 (Mþ, 100), 225 (67), 149 (55).
3.3.17. 2-Naphthyltrifluoromethanesulfonate (17).39 The
general procedure for synthesis of aryl triflate was used.
2-Naphthol (577 mg, 4.0 mmol), pyridine (1 mL,
12.0 mmol), triflic anhydride (0.7 mL, 4.2 mmol) and dry
dichloromethane (30 mL) were used to yield the 2-naphthyl-
trifluoromethansulfonate (17) (928 mg, 92%) as a colorless
liquid. Rf¼0.6 (hexane/ethyl acetate¼4:1); 1H NMR
(300 MHz, CDCl3) d 7.63 (dd, 1H, J¼1.3, 7.8 Hz), 7.59
(d, 1H, J¼7.9 Hz), 7.32–7.55 (m, 5H); MS (EI): m/z
(relative intensity) 276 (Mþ, 100), 143 (86).
3.3.12. 1-(Diphenylphosphino)-4-tert-butylbenzene
(12).42 4-tert-Butylphenyltrifluoro-methanesulfonate (11)
(141 mg, 0.5 mmol), palladium(II) acetate (11.2 mg,
0.05 mmol), triphenylphosphine (301 mg, 1.15 mmol) and
internal standard anthracene (89 mg, 0.5 mmol) were
dissolved in DMF (2 mL) in a Telfon screw-capped flask
under nitrogen. The reaction mixture was heated to 110–
1158C for 6 h and the color of the solution was changed
from pale yellow to orange. The reaction was cooled down
and the yield of 1-(diphenylphosphino)-4-tert-butylbenzene
(12) (50% GC yield) was determined by GC with respected
to the calibration curve of the authentic sample and
anthracene.
3.3.18. 2-(Diphenylphosphino)naphthalene (18).40
2-Naphthyltrifluoromethanesulfonate
(17)
(138 mg,
0.5 mmol), palladium(II) acetate (11.2 mg, 0.05 mmol),
triphenylphosphine (301 mg, 1.15 mmol), anthracene
(internal standard) (89 mg, 0.5 mmol), and DMF (2 mL)
were used to yield the 2-(diphenylphosphino)naphthalene
(18) (51% GC yield) was determined by GC with respected
to the calibration curve of the authentic sample and
anthracene.
3.3.13. 4-Methoxyphenyltrifluoromethanesulfonate
(13).39 The general procedure for synthesis of aryl triflate
was used. 4-Methoxyphenol (248 mg, 2.0 mmol), pyridine
(0.48 mL, 6.0 mmol), triflic anhydride (0.37 mL, 2.2 mmol)
and dry CH2Cl2 (15 mL) were used to yield 4-methoxy-
phenyltrifluoromethanesulfonate (13) (450 mg, 88%) as a
pale yellow liquid. Rf¼0.56 (hexane/ethyl acetate¼5:1); 1H
NMR (300 MHz, CDCl3) d 3.80 (s, 3H), 6.91 (d, 2H,
J¼9.0 Hz), 7.18 (d, 2H, J¼9.3 Hz), 7.28–7.31 (m, 1H); MS
(EI): m/z (relative intensity) 254 (Mþ, 33), 215 (11), 161
(17), 133 (49), 69 (100).
3.3.19. 3-Pyridyltrifluoromethanesulfonate (19).44
3-Hydroxypyridine (0.5 g, 5.3 mmol) was dissolved in
anhydrous dichloromethane (10 mL) under nitrogen at
room temperature followed by the addition of dry pyridine
(1.3 mL, 15.9 mmol). Triflic anhydride (0.98 mL,
5.8 mmol) in dichloromethane (3 mL) was then added
dropwise. The color of the solution was changed from
orange to red with white fume evolved. The reaction
mixture was allowed to stir at room temperature for one
hour. Water (20 mL) was added, extracted with dichloro-
methane (3£30 mL). The combined organic phase was
washed with water, brine and dried over MgSO4. The
residue was purified by short column chromatography on
silica gel to afford the 3-pyridyltrifluoromethanesulfonate
(19) (1.08 g, 90%) as a pale yellow oil. Rf¼0.3 (hexane/
ethyl acetate¼3:1); 1H NMR (300 MHz, CDCl3) d 8.52 (d,
1H, J¼1.5 Hz), 8.43 (d, 1H, J¼8.0 Hz), 7.66 (t, 1H,
J¼8.0 Hz), 7.35 (d, 1H, J¼7.9 Hz); MS (EI): m/z (relative
intensity) 227 (Mþ, 100), 158 (10), 94 (70).
3.3.14. 4-(Diphenylphosphino)anisole (14).43 Method A.
4-methoxyphenyl-trifluoromethanesulfonate (13) (128 mg,
0.5 mmol), palladium(II) acetate (11.2 mg, 0.05 mmol),
triphenylphosphine (301 mg, 1.15 mmol) and dry DMF
(2 mL) were used to yield 4-(diphenylphosphino)anisole
(14) (29 mg, 20%) as a white solid; mp 101–1048C (lit.43
1
101–1038C); H NMR (300 MHz, CDCl3) d 3.69 (s, 3H),
7.10 (dd, 2H, J¼4.0, 8.1 Hz), 7.24–7.59 (m, 12H); MS (EI):
m/z (relative intensity) 292 (Mþ, 100), 277 (12), 259 (10),
215 (30), 183 (48).
3.3.20. 3-(Diphenylphosphino)pyridine (20).34 3-Pyridyl
trifluoromethanesulfonate (19) (1.14 g, 5.0 mmol), palla-
dium(II) acetate (112 mg, 0.5 mmol), triphenylphosphine
(3.01 g, 11.5 mmol) were dissolved in dry DMF (20 mL) in
a Telfon screw-capped flask under nitrogen. The reaction
was heated to 110–1158C for 24 h and the color of the
solution was changed from pale yellow to deep red.
The reaction mixture was cooled down and filtered over a
short silica gel pad and the pad was washed by
dichloromethane. The aqueous extraction was performed
by using hydrochloric acid (3 M, 150 mL£5) and the
aqueous phase was collected and neutralized by sodium
carbonate solution to pH 7–8. The aqueous solution was
extracted by dichloromethane (50 mL£3). The combined
organic phase was washed with brine and dried over
MgSO4. The 3-(diphenylphosphino)pyridine (20) (263 mg,
20%) was obtained as the pale yellow solid. Rf¼0.8
(hexane/ethyl acetate¼5:1); mp¼98–1008C (lit. 98–
1008C); 1H NMR (300 MHz, CDCl3) d 8.34 (d, 1H,
J¼1.4 Hz), 8.30 (d, 1H, J¼8.3 Hz), 7.92 (t, 1H,
J¼8.2 Hz), 7.27–7.69 (m, 11H); MS (EI): m/z (relative
intensity) 263 (Mþ, 100), 186 (20).
3.3.15. 2-Methoxyphenyltrifluoromethanesulfonate
(15).39 The general procedure for synthesis of aryl triflate
was used. 2-Methoxyphenol (1.1 g, 10.0 mmol), pyridine
(2.4 mL, 20.0 mmol), triflic anhydride (1.9 mL, 11.0 mmol)
and dry CH2Cl2 (20 mL) were used to yield 2-methoxy-
phenyltrifluoromethanesulfonate (15) (2.1 g, 82%) as a
1
colorless liquid. Rf¼0.54 (hexane/ethyl acetate¼10:1); H
NMR (300 MHz, CDCl3) d 6.80 (t, 1H, J¼2.4 Hz), 6.85–
6.95 (m, 2H), 7.35 (t, 1H, J¼8.3 Hz); MS (EI): m/z (relative
intensity) 256 (Mþ, 27), 209 (58), 108 (100).
3.3.16. 2-(Diphenylphosphino)anisole (16).43 Method A.
2-Methoxyphenyltrifluoromethanesulfonate (15) (128 mg,
0.5 mmol), palladium(II) acetate (11 mg, 0.05 mmol),
triphenylphosphine (301 mg, 1.15 mmol) and dry DMF
(2 mL) were used to yield 2-(diphenylphosphino)anisole (16)
(40 mg, 28%)asawhite solid; mp95–988C (lit. 95–988C); 1H
NMR (300 MHz, CDCl3) d 3.48 (s, 3H), 7.05 (dd, 2H, J¼4.0,
8.1 Hz), 7.24–7.59 (m, 12H); MS (EI): m/z (relative intensity)
292 (Mþ, 100), 277 (18), 259 (12), 215 (30), 183 (48).

F. Y. Kwong et al. / Tetrahedron 59 (2003) 10295–10305
10303
3.3.21. 8-Quinonyltrifluoromethanesulfonate (21).45 The
general procedure of trifluoromethanesulfonation was used.
8-Hydroxylquinoline (0.5 g, 3.5 mmol), pyridine (0.83 mL,
10.4 mmol), triflic anhydride (0.64 mL, 3.8 mmol) and dry
dichloromethane (20 mL) were used to afford the 8-quino-
nyltrifluoromethanesulfonate (21) (878 mg, 92%) as a pale
yellow solid. Rf¼0.4 (hexane/ethyl acetate¼3:1); mp
(d, JCP¼14.8 Hz), 198.0; 31P NMR (162 MHz, CDCl3) d
212.88; MS (EI): m/z (relative intensity) 360 (Mþ, 100),
345 (8), 317 (12), 253 (8), 241 (15), 225 (13), 211 (22), 193
(16); HRMS (ESIMS) calcd for C24H25OPHþ 361.1721,
found 361.1709.
3.3.26. 4-(Di(4-methoxyphenyl)phosphino)acetophenone
(30). Method A was followed. 4-Acetylphenyltriflate (1)
(1.0 mmol), palladium acetate (22.4 mg, 0.1 mmol), tri(4-
methoxyphenyl)phosphine (810 mg, 2.3 mmol) and dry
DMF (4 mL) were used to yield 4-(di(4-methoxyphenyl)-
phosphino)acetophenone (30) (120 mg, 33%) as pale yellow
solid after purified by column chromatography on silica gel
using a solvent mixture (hexane/ethyl acetate¼10:1) as the
eluent. Rf¼0.2 (hexane/ethyl acetate¼10:1); mp 54–568C;
1H NMR (300 MHz, CDCl3) d 2.57 (s, 3H), 3.81 (s, 6H),
6.90 (dd, 4H, J¼6.0, 2.1 Hz), 7.25–7.32 (m, 6H), 7.85 (dd,
2H, J¼8.4, 1.5 Hz); 13C NMR (75 MHz, CDCl3) d 26.6,
55.2, 114.3 (d, JCP¼8.3 Hz), 127.1 (d, JCP¼7.4 Hz), 127.8
1
70–738C (lit.45 70–728C); H NMR (300 MHz, CDCl3) d
8.50 (d, 1H, J¼1.5 Hz), 7.87 (d, 1H, J¼8.1 Hz), 7.34–7.67
(m, 4H); MS (EI): m/z (relative intensity) 277 (Mþ, 100),
144 (54).
3.3.22. 8-(Diphenylphosphino)quinoline (22).34 8-
Quinolyltrifluoromethanesulfonate
(21)
(554 mg,
2.0 mmol), palladium(II) acetate (45 mg, 0.2 mmol), tri-
phenylphosphine (1.21 g, 4.6 mmol) were dissolved in dry
DMF (8 mL) in a Telfon screw-capped flask under nitrogen.
The reaction was heated to 110–1158C for 72 h and the
color of the solution was changed from yellow to red. The
reaction mixture was cooled down and concentrated by
reduced pressure. The residue was purified by column
chromatography on silica gel using a solvent mixture
(hexane/ethyl acetate¼5:1) as eluent to afford 8-(diphenyl-
phosphino)quinoline (22) (282 mg, 45%) as the pale yellow
solid. Rf¼0.5 (hexane/ethyl acetate¼5:1); mp 134–1368C
(lit. 133–1368C); 1H NMR (300 MHz, CDCl3) d 7.10–7.14
(m, 1H), 7.26–7.43 (m, 12H), 7.78 (d, 1H, J¼8.0 Hz), 8.12
(d, 1H, J¼8.2 Hz), 8.85 (dd, 1H, J¼1.6, 4.2 Hz), 31P NMR
(162 MHz, CDCl3) d 215.11; MS (EI): m/z (relative
intensity) 313 (Mþ, 100), 235 (60), 204 (51), 183 (32),
159 (30).
(d, JCP¼5.8 Hz), 132.6 (d, JCP¼17.7 Hz), 135.5 (d, JCP
¼
21.5 Hz), 136.3, 146.1 (d, JCP¼13.9 Hz), 160.5, 197.8; 31P
NMR (162 MHz, CDCl3) d 213.03; MS (EI): m/z (relative
intensity) 364 (Mþ, 100), 349 (10), 281 (9), 257 (10), 245
(30), 229 (8), 214 (40), 199 (18); HRMS (ESIMS) calcd for
C22H21O3PHþ 365.1307, found 365.1289.
3.3.27.
Method
4-(Di(4-tolyl)phosphino)acetophenone (31).
A was followed. 4-Acetylphenyltriflate (1)
(1.0 mmol), palladium acetate (22.4 mg, 0.1 mmol), tri(4-
tolyl)phosphine (699 mg, 2.3 mmol) and dry DMF (4 mL)
were used to obtain 4-(di(4-tolyl)phosphino)acetophenone
(31) (129 mg, 39%) as light yellow solid after purified by
column chromatography on silica gel using a solvent
mixture (hexane/ethyl acetate¼10:1) as the eluent. Rf¼0.4
(hexane/ethyl acetate¼10:1); mp 58–608C; 1H NMR
(300 MHz, CDCl3) d 2.35 (s, 6H), 2.57 (s, 3H), 7.15–7.25
(m, 8H), 7.36 (dd, 2H, J¼8.4, 1.5 Hz), 7.86 (dd, 2H, J¼8.4,
1.5 Hz); 13C NMR (75 MHz, CDCl3) d 21.3, 26.6, 127.9 (d,
3.3.23. 4-Nitrophenyltrifluoromethanesulfonate (23).46
As shown in general procedure.
3.3.24. 1,4-Ditrifluoromethanesulfonyloxybenzene
(25).39 The general procedure for synthesis of aryl triflate
was used. 1,4-Dihydroxybenzene (550 mg, 5.0 mmol),
pyridine (2.4 mL, 30.0 mmol), triflic anhydride (2 mL,
12.0 mmol) and dry CH2Cl2 (20 mL) were used to yield
1,4-ditrifluoromethanesulfonyloxybenzene (25) (1.8 g, 95
%) as a white solid. After purified by column chromato-
graphy on silica gel using a solvent mixture (hexane/ethyl
acetate¼5:1) as the eluent. Rf¼0.74 (hexane/ethyl
acetate¼5:1); mp 53–558C (lit. 52–558C); 1H NMR
(300 MHz, CDCl3) d 7.4 (s, 4H); MS (EI): m/z (relative
intensity) 374 (Mþ, 43), 189 (100), 133 (49).
JCP¼6.0 Hz), 129.5 (d, JCP¼7.5 Hz), 132.7 (d, JCP
¼
9.0 Hz), 133.0 (d, JCP¼18.2 Hz), 134.0 (d, JCP¼20.3 Hz),
136.5, 139.2, 145.3 (d, JCP¼14.3 Hz), 197.8; 31P NMR
(162 MHz, CDCl3) d 212.60; MS (EI): m/z (relative
intensity) 332 (Mþ, 100), 317 (5), 289 (10), 281 (7), 241
(8), 211 (30), 197 (28); HRMS (ESIMS) calcd for
C22H21OPHþ 333.1408, found 333.1385.
3.3.28. 3-(Diphenylphosphino)benzaldehyde (35).47
Method B was followed. Yield 38%. Rf¼0.6 (hexane/ethyl
1
3.3.25. 4-(Bis(3,5-dimethylphenyl)phosphino)aceto-
phenone (29). Method A was followed. 4-Acetylphenyl-
triflate (1) (1.0 mmol), palladium(II) acetate (22.4 mg,
0.1 mmol), trixylylphosphine (796 mg, 2.3 mmol) and dry
DMF (4 mL) were used to yield 4-(bis(3,5-dimethyl)-
phosphino)acetophenone (29) (122 mg, 34%) as pale yellow
solid after purified by column chromatography on silica gel
using a solvent mixture (hexane/ethyl acetate¼10:1) as the
eluent. Rf¼0.6 (hexane/ethyl acetate¼10:1); mp 56–588C;
1H NMR (300 MHz, CDCl3) d 2.27 (s, 12H), 2.59 (s, 3H),
6.93 (s, 2H), 6.96 (s, 2H), 7.00 (s, 2H), 7.34 (dd, 2H,
J¼8.3 Hz, 1.4 Hz), 7.87 (dd, 2H, J¼8.3, 1.4 Hz); 13C NMR
(75 MHz, CDCl3) d 21.3, 26.6, 127.9 (d, JCP¼6.2 Hz),
131.0, 131.7 (d, JCP¼20.2 Hz), 133.2 (d, JCP¼18.2 Hz),
135.7 (d, JCP¼9.5 Hz), 136.5, 138.1 (d, JCP¼7.9 Hz), 145.1
acetate¼10:1); H NMR (300 MHz, CDCl3) d 7.32–7.43
(m, 12H), 7.80 (dd, 2H, J¼8.1, 1.5 Hz), 10.00 (s, 1H); 13C
NMR (75 MHz, CDCl3) d 128.8 (d, JCP¼7.2 Hz), 129.3,
133.5 (d, JCP¼18.3 Hz), 134.0 (d, JCP¼20.0 Hz), 135.7 (d,
JCP¼10.4 Hz), 136.0, 146.5 (d, JCP¼15.5 Hz), 191.9; 31P
(162 MHz, CDCl3) d 23.41; MS (EI): m/z (relative
intensity) 290 (Mþ, 100), 261 (8), 211 (9), 183 (95), 165
(12), 152 (20).
Acknowledgements
The work described in this paper was supported by the
Area of Excellence Scheme established under the
University Grants Committee of the Hong Kong Special

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F. Y. Kwong et al. / Tetrahedron 59 (2003) 10295–10305
19. Previous synthesis of 4-(diphenylphosphino)benzonitirle and
methyl 4-(diphenylphosphino)benzoate required a three-steps
route and the overall yields were approximately 11 and 21%,
respectively. (a) Chou, W. N.; Pomerantz, M. J. Org. Chem.
1991, 56, 2762–2766. (b) Schiemenz, G. P.; Siebeneich, H. U.
Chem. Ber. 1969, 102, 1883–1888. (c) Aexandrovich, P.S.;
DeMejo, L.P.; Jadwin, T.A.; Wilson, J.C. US Patent 4,837,
394, 1989..
Administrative Region, Hong Kong, China, (Project No.
[AoE/P-10/01]).
References
1. Kosolapoff, G. M.; Maier, L. Organic Phosphorous Com-
pounds; 2nd ed. Wiley/Interscience: New York, 1972.
20. Hu, W. H.; Chen, C. C.; Xue, G. P.; Chan, A. S. C.
Tetrahedron: Asymmetry 1998, 9, 4183–4192.
2. (a) In Metal-catalyzed Cross-coupling Reactions; Diederich,
F., Stang, P. J., Eds.; Wiley-VCH: Germany, 1998. (b) Tsuji, J.
Palladium Reagents and Catalysts; Wiley: Chichester, 1995.
3. For some examples using organometallic approach to the
synthesis of phosphine ligands, see: (a) Takaya, H.; Mashima,
K.; Koyano, K.; Yagi, M.; Kumobayaashi, H.; Taketomi, T.;
Akutagawa, S.; Noyori, R. J. Org. Chem. 1986, 51, 629–634.
(b) Takaya, H.; Akutagawa, S.; Noyori, R. Org. Synth. 1989,
67, 20–32. (c) Gelpke, A. E. S.; Kooijman, H.; Spek, A. L.;
Hiemstra, H. Chem. Eur. J. 1999, 5, 2472–2480.
21. (a) Davies, J. A.; Hartley, F. R. Chem. Rev. 1979, 79,
2658–2678. For recent application, see: (b) Francio, G.;
Faraone, F.; Leitner, W. Angew. Chem. Int. Ed. 2000, 39,
1428–1430.
22. Kwong, F. Y.; Lai, C. W.; Chan, K. S. Tetrahedron Lett. 2002,
43, 3537–3539.
23. Morita, D. K.; Stille, J. K.; Norton, J. R. J. Am. Chem. Soc.
1995, 117, 8576–8581.
¨
24. For examples: (a) Piber, M.; Jensen, A. E.; Rottlander, M.;
Knochel, P. Org. Lett. 1999, 1, 1323–1326. (b) Dai, W.-M.;
Guo, D.-S.; Sun, L.-P. Tetrahedron Lett. 2001, 42,
5275–5278. (c) Herrmann, W. A.; Brossmer, C.; Reisinger,
4. For recent references, see: (a) Martorell, G.; Garcias, X.;
´
Janura, M.; Saa, J. M. J. Org. Chem. 1998, 63, 3463–3467.
(b) Ding, K.; Wang, Y.; Yun, H.; Liu, J.; Wu, Y.; Terada, M.;
Okubo, Y.; Mikami, K. Chem. Eur. J. 1999, 5, 1734–1736.
ˇ ˇ ˇ ´ˇ
(c) Vyskocil, S.; Smrcina, M.; Hanus, V.; Polasek, M.;
¨
C.-P.; Riedermeier, T. H.; Ofele, K.; Beller, M. Chem. Eur. J.
1997, 3, 1357–1361. (d) Powell, N. A.; Rychnovsky, S. D.
Tetrahedron Lett. 1996, 37, 7901–7904. (e) Nakamura, K.;
Okubo, H.; Yamaguchi, M. Synlett 1999, 549–552.
(f) Albanese, D.; Landini, D.; Penso, M.; Petricci, S. Synlett
1999, 199. (g) Nguefack, J.-F.; Bollit, V.; Sinou, D.
Tetrahedron Lett. 1996, 37, 5527–5530. (h) Wright, S. W.;
Hageman, D. L.; McClure, L. D. J. Org. Chem. 1994, 59,
6095–6099.
ˇ
´
Kocovsky, P. J. Org. Chem. 1998, 63, 7738–7748.
5. Kurtz, L.; Lee, G.; Morgan, D., Jr.; Waldayke, M. J.; Ward, T.
Tetrahedron Lett. 1990, 31, 6321–6324.
6. Bringmann, G.; Wuzik, A.; Vedder, C.; Pfeiffer, M.; Stalke, D.
Chem. Commun. 1998, 1211–1212.
7. Lipshutz, B. H.; Buzard, D. H.; Yun, C. S. Tetrahedron Lett.
1999, 40, 201–204.
25. Grushin, V. V. Organometallics 2000, 19, 1888–1900, and
references therein.
8. (a) Oshiki, T.; Imamoto, T. J. Am. Chem. Soc. 1992, 114,
3975–3977. (b) Imamoto, T.; Oshiki, T.; Onozawa, T.;
Kusumoto, T.; Sato, K. J. Am. Chem. Soc. 1990, 112,
5244–5252.
26. Amatore, C.; Jutand, A.; M’Barki, M. A. Organometallic
1992, 11, 3009–3013.
´
27. Amatore, C.; Carre, E.; Jutand, A.; M’Barki, M.; Meyer, G.
Organometallics 1995, 14, 5605–5614.
9. Brisset, H.; Gourdel, Y.; Pellon, P.; Le Corre, M. Tetrahedron
Lett. 1993, 34, 4523–4526.
28. Amotore, C.; Jutand, A. Acc. Chem. Res. 2000, 33, 314–321,
and references therein.
10. (a) Gilbertson, S. R.; Starkey, G. W. J. Org. Chem. 1996, 61,
2922–2923. (b) Kraatz, H.-B.; Pletsch, A. Tetrahedron:
Asymmetry 2000, 11, 1617–1623.
29. (a) Migita, T.; Nagai, T.; Kiuchi, K.; Kosugi, M. Bull. Chem.
Soc. Jpn 1983, 56, 2869–2870. (b) Sakamoto, M.; Shimizu, I.;
Yamamoto, A. Chem. Lett. 1995, 1101–1102. (c) Hinkle, R. J.;
Stang, P. J.; Kowalalski, M. H. J. Org. Chem. 1990, 55,
5033–5035. (d) Ziegler, C. B., Jr.; Heck, R. F. J. Org. Chem.
1978, 43, 2941–2946. (e) de la Torre, G.; Gouloumis, A.;
11. (a) Cai, D.; Payack, J. F.; Bender, D. R.; Hughes, D. L.;
Verhoeven, T. R.; Reider, P. J. J. Org. Chem. 1994, 59,
7180–7181. (b) Cai, D.; Payack, J. F.; Bender, D. R.; Hughes,
D. L.; Verhoeven, T. R.; Reider, P. J. Org. Synth. 1998, 76,
6–11. (c) Cai, D.; Payack, J. F.; Verhoeven, T. R. US Patent 5,
399,711..
´
Vazquez, P.; Torres, T. Angew. Chem. Int. Ed. 2001, 40,
2895–2898.
12. Ager, D. J.; East, M. B.; Eisenstadt, A.; Laneman, S. Chem.
Commun. 1997, 2359–2360.
30. (a) Goodson, F. E.; Wallow, T. I.; Novak, B. M. J. Am. Chem.
Soc. 1997, 119, 12441–12453. (b) Kong, K. C.; Cheng, C. H.
J. Am. Chem. Soc. 1991, 113, 6313–6315.
13. (a) Kwong, F. Y.; Chan, K. S. Chem. Commun. 2000,
1069–1070. (b) For correction, see: Kwong, F. Y.; Chan,
K. S. Chem. Commun. 2000, 1447–1447.
31. For review, see: (a) Garrou, P. E. Chem. Rev. 1985, 85,
171–185. For selective aryl-P/aryl-Pd exchange instead of
alkyl-P/aryl-Pd exchange, see: (b) Morita, D. K.; Stille, J. K.;
Norton, J. R. J. Am. Chem. Soc. 1995, 117, 8576–8581.
32. Tebby, J. C. Handbook of Phosphorus-31 Nuclear Magnetic
Resonance Data; CRC: Boca Raton, FL, 1991; p 219.
33. Perrin, D. D.; Armarego, L. F. Purification of Laboratory
Chemicals; 3rd ed., 1988.
14. (a) Kwong, F. Y.; Lai, C. W.; Tian, Y.; Chan, K. S.
Tetrahedron Lett. 2000, 41, 10285–10289. (b) Kwong, F. Y.;
Chan, K. S. Organometallics 2000, 19, 2058–2060.
15. Kwong, F. Y.; Chan, K. S. Organometallics 2001, 20,
2570–2578.
16. Malmstrom, T.; Weigl, H.; Andersson, C. Organometallics
1995, 14, 2593–2596.
¨ ¨
17. Markl, G.; Reiss, M.; Kreitmeier, P.; Noth, H. Angew. Chem.
34. Kwong, F. Y.; Lai, C. W.; Tian, Y.; Chan, K. S. Tetrahedron
Lett. 2000, 10285–10289.
35. Tunney, S. E.; Stille, J. K. J. Org. Chem. 1987, 52, 748–753.
¨ ¨
36. Markl, G.; Reiss, M.; Kreitmeier, P.; Noth, H. Angew. Chem.
Int. Ed. Engl. 1995, 34, 2230–2234.
Int. Ed. Engl. 1995, 34, 2230–2232.
18. (a) Hoots, J. E.; Rauchfuss, T. B.; Wrobleski, D. A. Inorg.
Synth. 1982, 21, 175–178. (b) Schiemenz, G. P.; Kaack, H.
Leibigs Ann. Chem. 1973, 1494–1499.

F. Y. Kwong et al. / Tetrahedron 59 (2003) 10295–10305
10305
37. Ravindar, V.; Hemling, H.; Schumann, H.; Blum, J. Synth.
Commun. 1992, 22, 841–851.
metallics 1992, 11, 3588–3600. (b) Hall, C. D.; Tweedy, B. R.;
Kayhanian, R.; Lloyd, J. R. J. Chem. Soc. Perkin Trans. 2
1992, 775–779.
38. Aexandrovich, P. S.; DeMejo, L. P.; Jadwin, T. A.; Wilson,
J. C. US Patent 4,837,394, 1989..
44. (a) Sonesson, C.; Larhed, M.; Nyqvist, C.; Hallberg, A. J. Org.
´
Chem. 1986, 61, 4756–4763. (b) Saa, J. M.; Dopico, M.;
39. Stang, P. J.; Hanack, M.; Subramanian, L. R. Synthesis 1982,
85–126.
Martorell, G.; Garcia-Raso, A. J. Org. Chem. 1990, 65,
991–997.
40. Bethell, D.; Bourne, R.; Kasran, M. J. Chem. Soc. Perkin
Trans. 2 1994, 2081–2084.
45. Badone, D.; Guzzi, U. Tetrahedron Lett. 1993, 34,
3603–3606.
41. Larhed, M.; Andersson, C. M.; Hallberg, A. Tetrahedron
1994, 50, 285–304.
46. Cabri, W.; Candiani, I.; Bedeschi, A.; Penco, S.; Santi, R.
J. Org. Chem. 1992, 57, 1481–1486.
42. Brune, H. A.; Falck, M.; Hemmer, R. Chem. Ber. 1984, 117,
2791–2802.
43. (a) Burgess, K.; Ohimeyer, M. J.; Whitmire, K. H. Organo-
47. Schiemenz, G. P.; Kaack, H. Leibigs Ann. Chem. 1973, 9,
1480–1493.