nBuLi-mediated hydrophosphination: A simple route to valuable organophosphorus compounds

Article abstract of DOI:10.1002/ejoc.200901407

A straightforward synthesis of homoallyl- and allylphosphanes has been developed using nBuLi-mediated hydrophosphination of conjugated dienes. In all the cases the phosphorus atom of the reacting phosphane attacked the sterically less demanding side of the diene exclusively. In addition, high regioselectivities towards 1,2- or 1,4-addition products were observed depending on the nature of the dienes. This hydrophosphination reaction was extended to a variety of substrates such as styrene derivatives, alkynes and 1,3,5-cycloheptatriene. The structures of three hydrophosphination products were confirmed by X-ray diffraction studies.

Full text of DOI:10.1002/ejoc.200901407

FULL PAPER
DOI: 10.1002/ejoc.200901407
nBuLi-Mediated Hydrophosphination: A Simple Route to Valuable
Organophosphorus Compounds
Arnaud Perrier,[a] Virginie Comte,[a] Claude Moïse,[a] Philippe Richard,[a] and
Pierre Le Gendre*[a]
Keywords: Alkenes / Alkynes / Hydrophosphination / Ligand design / Phosphorus
A straightforward synthesis of homoallyl- and allylphos-
products were observed depending on the nature of the
phanes has been developed using nBuLi-mediated hydro- dienes. This hydrophosphination reaction was extended to a
phosphination of conjugated dienes. In all the cases the
phosphorus atom of the reacting phosphane attacked the
sterically less demanding side of the diene exclusively. In ad-
dition, high regioselectivities towards 1,2- or 1,4-addition
variety of substrates such as styrene derivatives, alkynes and
1,3,5-cycloheptatriene. The structures of three hydrophos-
phination products were confirmed by X-ray diffraction
studies.
Introduction
Results and Discussion
We recently described the first titanium-catalysed 1,4-
hydrophosphination of conjugated dienes, which afforded
allylphosphanes in good yields and regioselectivities.[9]
Searching for ways to improve this process, we noticed
that the presence of an excess of nBuLi, originally used as
a catalyst activator, reduced the regioselectivity of the reac-
tion leading to a mixture of 1,2- and 1,4-addition products.
We therefore started to explore the hydrophosphination of
1,3-dienes in the sole presence of nBuLi. In an initial experi-
ment we carried out the reaction of isoprene with PPh2H
in toluene in the presence of 15 mol-% nBuLi (Scheme 1).
The reaction mixture was stirred at room temperature and
monitored by GC analysis. Surprisingly, no remaining di-
phenylphosphane was detected after only 2 h. NMR analy-
sis of the products obtained after sulfidation showed that
hydrophosphination of isoprene had occurred, leading al-
most exclusively to the homoallylphosphane sulfide 1a.
Alkenylphosphanes are a promising class of ligand pre-
cursors for catalysis.[1] Indeed, these mixed bidentate li-
gands can lead to stable but nonetheless highly active cata-
lytic systems thanks to the combination of two electroni-
cally different binding sites in a single ligand framework
and to the presumed lability of the C–C double bond, which
can readily and reversibly dissociate from the active metal
centre. Thus, there is considerable interest in developing fac-
ile and efficient syntheses of these ligands. Alkenylphos-
phanes can be readily prepared by nucleophilic substitution
using either phosphide anions or halogenophosphanes. An
alternative atom-economic route towards these compounds
involves the hydrophosphination of alkynes and conjugated
dienes to form either vinyl-, allyl- or homoallylphos-
phanes.[2] These reactions can be achieved under radical ac-
tivation,[3] in basic conditions[4] or alternatively in the pres-
ence of group 2,[5] late-transition-metal[6] and lanthanide-
based[7] catalysts. The use of phosphane–borane complexes
under neutral conditions has also been described.[8] How-
ever, most of the above-mentioned reactions suffer from
certain limitations, such as the availability of catalysts, the
narrow scope of substrates and a lack of selectivity. We re-
port herein a simple and efficient base-promoted hydro-
phosphination of a variety of 1,3-dienes using several phos-
phanes and yielding alkenylphosphanes with high regio-
selectivities. Moreover, this simple procedure has been ap-
plied to alkynes, unactivated olefins and cyclo-1,3,5-hepta-
triene.
[a] Institut de Chimie Moléculaire de l’Université de Bourgogne,
ICMUB-UMR CNRS 5260, Université de Bourgogne,
9 avenue Alain Savary, BP 47870, 21078 Dijon Cedex, France
Fax: +33-380396098
E-mail: pierre.le-gendre@u-bourgogne.fr
Scheme 1. nBuLi-mediated hydrophosphination of isoprene.
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Eur. J. Org. Chem. 2010, 1562–1568

nBuLi-Mediated Hydrophosphination Reactions
This result explains the detrimental effect of an excess Table 1. nBuLi-mediated hydrophosphination of a variety of dienes
and phosphanes.[a]
of nBuLi on the regioselectivity of the titanium-catalysed
hydrophosphination reaction,[9] the first highly 1,2-regiose-
lective hydrophosphination of isoprene reported to date.[10]
Crystals of 1a suitable for X-ray measurements were ob-
tained and confirmed the homallylic structure of the phos-
phane (Figure 1).
Figure 1. Molecular structure of the homoallylphosphane sulfide
1a.
Different solvents were then screened and toluene proved
to be the best as addition of PPh2H to isoprene in the pres-
ence of 15 mol-% nBuLi took place in Et2O, THF and
DMSO but with lower regioselectivities (1a/2a ratio 81:19,
72:28 and 51:49, respectively). The same reaction performed
in hexane resulted in no conversion. Experiments in ionic
liquids such as 1-butyl-2,3-dimethylimidazolium bis-trifl-
imide [BDMIM][NTf2][11] were also not convincing (low
yields and selectivities). In addition, hydrophosphination of
isoprene was completed in 1 h at 70 °C but with the oppo-
site regioselectivity (1a/2a ratio: 40:60).[12] Thus, detrimen-
tal effects of solvent polarity and of reaction temperature
[a] Reaction conditions: toluene (2 mL), phosphane (1.25 mmol),
nBuLi (0.19 mmol) and diene (3.75 mmol).
on the regioselectivity of the hydrophosphination reaction
were observed. These results might be explained on the ba- homoallylphosphanes 1d and 1e in good yields and selec-
sis that polar solvents stabilize the ionic intermediates, tivities (entries 4 and 5). 2,3-Dimethyl-1,3-butadiene re-
which favours the thermodynamic 1,4-addition product, as quired a prolonged reaction time and a higher reaction tem-
does high temperatures. Note that attempts to reduce or to perature to go to completion and led exclusively to the allyl-
increase the amount of nBuLi (5–40 mol-%) rendered the phosphanes 2f and 2g (entries 6 and 7). This opposite re-
reaction slower. Finally, the use of a stoichiometric amount gioselectivity can be explained in terms of thermodynamic
of nBuLi led to no conversion as was reported in the parent control taking precedence under these more severe condi-
nBuLi-mediated hydroamination reaction.[14] After showing tions. The use of (1R)-nopadiene as a substrate provided
that the initial experimental conditions were indeed the a straightforward route to the chiral homoallylphosphane
best, we explored the scope of the nBuLi-mediated hydro- sulfide 1h (entry 8). Cyclic dienes such as 1,3-cyclohexa-
phosphination reaction with a variety of dienes and phos- diene underwent hydrophosphination at 70 °C but without
phanes (Table 1).
showing any selectivity (entry 9).
As highlighted in Table 1, all the hydrophosphination
This hydrophosphination reaction was then applied to a
products were obtained in high yields. The electron-rich variety of C–C multiple bonds (Table 2). The hydrophos-
methylphenyl- and dicyclohexylphosphanes participated in phination of styrene with PPh2H yielded (2-phenylethyl)di-
the hydrophosphination of isoprene although the reactions phenylphosphane sulfide (3) after 16 h at 70 °C and the
rates were somewhat slower (entries 1–3). The regioselectivi- usual work-up (entry 1). The addition of PCy2H to styrene
ties reached in these reactions were high and similar to under similar conditions afforded the hydrophosphination
those obtained with PPh2H. Hydrophosphination of myr- product 4 in good yield (entry 2). At this point it is worth
cene with PPh2H and PPhMeH was facile and gave the mentioning that the system tBuOK/DMSO allowed this re-
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A. Perrier, V. Comte, C. Moïse, P. Richard, P. Le Gendre
FULL PAPER
action under milder conditions (room temp., 1 h) but led to
the phosphane oxide.[4e] More hindered substrates such as
1,1-diphenylethylene underwent hydrophosphination to
give the linear product 5 selectively (entry 3). The opposite
regioselectivity was observed by using α-methylstyrene as
the substrate (entry 4). This was probably due to the lack
of stability of the α-carbanion intermediate such that the
phosphide added to the α position instead, creating a more
stable primary carbanion at the β position.
Table 2. Substrate scope of the nBuLi-mediated hydrophosphina-
tion reaction.[a]
Figure 2. Molecular structure of (Z)-styryldiphenylphophane sul-
fide (7).
a solid and was thus easy to isolate as the free phosphane
by simple recrystallization of the crude product in pentane.
An X-ray diffraction study was performed on suitable crys-
tals and confirmed the structure of the phosphanyldiene
(Figure 3). The cycloheptadiene ring exhibits an asymmetri-
cally distorted conformation, as illustrated by the following
torsion angles [C1–C2–C3–C4 56.4(4)°, C3–C4–C5–C6
–20.2(6)° and C5–C6–C7–C1 –0.6(5)°] and the diphenyl-
phosphanyl group is located in the exo position.
[a] Reaction conditions: toluene (2 mL), phosphane (1.25 mmol),
nBuLi (0.19 mmol) and substrate (3.75 mmol). [b] The partial te-
lomerization of styrene was observed. [c] Z/E ratio: 60:40.
Efforts to achieve the hydrophosphination of 1-hexene
met with more limited success (6% yield, 3 d, 70 °C). On
the other hand, the hydrophosphination reaction could be
extended to alkynes;[13] diphenylphosphane added to phen-
ylacetylene in the presence of 15 mol-% nBuLi in toluene
to give (Z)-styryldiphenylphosphane sulfide (7) as the main
product (entry 5).[15] The Z configuration of the major iso-
Figure 3. Molecular structure of (3,5-cycloheptadienyl)diphenyl-
phosphane sulfide (9).
Conclusions
1
mer was determined by H NMR spectroscopy and con-
We have described a simple and efficient method for the
firmed by an X-ray diffraction study. An ORTEP view of 7 hydrophosphination of conjugated dienes mediated by
is shown in Figure 2. 15 mol-% nBuLi. The reactions were applied to a variety of
The reaction of diphenylacetylene under similar condi- dienes and phosphanes and gave the hydrophosphination
tions afforded the alkenylphosphane 8 in good yield but products as phosphane sulfides in high yields after sulfid-
with modest diastereoselectivity (entry 6).[16] Finally, the ation work-up. The regioselectivity of the process is remark-
use of 1,3,5-cycloheptatriene as the substrate provided (3,5- able. In all cases, the phosphorus atom of the reacting phos-
cycloheptadienyl)diphenylphosphane sulfide (9) in excellent phane attacked the sterically less demanding side of the
yield after the usual work-up (entry 7). Interestingly, no diene exclusively. In addition, high regioselectivities towards
double hydrophosphination product was observed under 1,2- or 1,4-addition products were observed depending on
these conditions. Further, the hydrophosphination of cyclo- the nature of the dienes. Finally, this hydrophosphination
heptatriene could be scaled up to several grams and re- reaction can be applied to a variety of substrates, such as
quired no special conditions. The corresponding adduct is styrene derivatives, alkynes and 1,3,5-cycloheptatriene.
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Eur. J. Org. Chem. 2010, 1562–1568

nBuLi-Mediated Hydrophosphination Reactions
2JCP = 3.8 Hz, 2 C, CH2), 31.0 (d, 3JCP = 3 Hz, 1 C, CH2), 38.7 (d,
Most of the phosphanes prepared in this study were iso-
lated as the free phosphanes and readily used as ligands
after simple evaporation of the solvent and of the excess
diene. Preliminary studies have been carried out specifically
with ruthenium complexes and will be published in due
course.
4
1JCP = 47.5 Hz, 1 C, CH), 110.1 (s, 1 C, C=CH2), 145.1 (d, JCP
=
13.6 Hz, 1 C, C=CH2) ppm. C17H31PS (298.5): calcd. C 68.41, H
10.47, S 10.74; found C 68.42, H 10.44, S 10.69.
(7-Methyl-3-methylene-6-octenyl)diphenylphosphane Sulfide (1d):
Colourless oil (416 mg, 94% yield). Rf = 0.5 (pentane/Et2O, 9:1).
31P{1H} NMR (CDCl3): δ = 42.7 (s, PPh2) ppm. 1H NMR
(CDCl3): δ = 1.58 [s, 3 H, =C(CH3)2], 1.68 [s, 3 H, =C(CH3)2],
2.02–2.11 (m, 4 H, CH2), 2.33 (m, 2 H, CH2), 2.59 (m, 2 H, CH2P),
4.79 (pseudo s, 2 H, =CH2), 5.07 (m, 1 H, CH), 7.44–7.53 (m, 6
H, Ph), 7.82–7.90 (m, 4 H, Ph) ppm. 13C{1H} NMR (CDCl3): δ =
17.8 [s, 1 C, =C(CH3)2], 25.7 [s, 1 C, =C(CH3)2], 26.3 (s, 1 C, CH2),
Experimental Section
General: All reactions were carried out under purified argon using
vacuum line techniques. Solvents were dried and distilled under
argon from sodium before use. Elemental analyses were performed
with an EA 1108 CHNS-O FISONS Instrument. 1H (300.13 MHz),
13C (75.4 MHz) and 31P (121.13 MHz) NMR spectra were recorded
with a Bruker 300 Avance spectrometer. Chemical shifts are quoted
in ppm (δ) relative to TMS (1H, 13C) or external H3PO4 (31P). Cou-
pling constants are reported in Hz.
2
1
28.4 (d, JCP = 1.6 Hz, 1 C, CH2), 31.1 (d, JCP = 56.3 Hz, 1 C,
CH2), 36.1 (s, 1 C, CH2), 109.52 (s, 1 C, =CH2), 123.7 (s, 1 C,
2
3
=CH), 128.7 (d, JCP = 11.8 Hz, 4 C, o-Ph), 131.1 (d, JCP
=
4
10.1 Hz, 4 C, m-Ph), 131.5 (d, JCP = 3.0 Hz, 2 C, p-Ph), 131.9 [s,
1
1 C, =C(CH3)2], 132.7 (d, JCP = 80.1 Hz, 2 C, ipso-Ph), 148.40 (d,
3JCP = 16.7 Hz, 1 C, C=CH2) ppm. C22H27PS (354.49): calcd. C
74.54, H 7.68, S 9.05; found C 74.88, H 7.43, S 9.11.
Typical Procedure for nBuLi-Mediated Hydrophosphination: In a
Schlenk tube, a nBuLi solution (0.19 mmol, 1.6  in hexanes) was
added to a solution of PR2H (1.25 mmol) in freshly distilled tolu-
ene (2 mL). The solution was stirred for 30 min at room tempera-
ture and then the diene (3.75 mmol) was added. The reaction mix-
ture was stirred until full consumption of PR2H (monitored by
GC). S8 (0.16 mmol) was then added and the reaction mixture was
stirred at room temperature for 3 h. The products were purified by
silica gel chromatography.
(7-Methyl-3-methylene-6-octenyl)(methyl)phenylphosphane Sulfide
(1e): Colourless oil (336 mg, 92% yield). Rf = 0.5 (pentane/Et2O,
9:1). 31P{1H} NMR (CDCl3): δ = 37.8 (s, PMePh) ppm. H NMR
1
(CDCl3): δ = 1.58 [s, 3 H, =C(CH3)2], 1.68 [s, 3 H, =C(CH3)2], 1.99
2
(d, JPH = 12.6 Hz, 3 H, P-CH3), 2.03–2.06 (m, 4 H, CH2), 2.19–
2.29 (m, 4 H, CH2), 4.74 (s, 1 H, =CH2), 4.78 (s, 1 H, =CH2), 5.06
(m, 1 H, C=CH), 7.40–7.60 (m, 3 H, Ph), 7.81–7.90 (m, 2 H,
Ph) ppm. 13C{1H} NMR (CDCl3): δ = 17.7 [s, 1 C, =C(CH3)2],
20.8 (d, 1JCP = 55.8 Hz, 1 C, P-CH3), 25.6 [s, 1 C, =C(CH3)2], 26.1
(3-Methyl-3-butenyl)diphenylphosphane Sulfide (1a): White solid
(347 mg, 97% yield, m.p. 76 °C). Rf = 0.6 (pentane/Et2O, 9:1).
31P{1H} NMR (CDCl3): δ = 42.7 (s, PPh2) ppm. 1H NMR
(CDCl3): δ = 1.74 (s, 3 H, =CCH3), 2.31 (m, 2 H, =CCH2), 2.60
(m, 2 H, CH2P), 4.74 (s, 1 H, =CH2), 4.78 (s, 1 H, =CH2), 7.44–
7.54 (m, 6 H, Ph), 7.82–7.90 (m, 4 H, Ph) ppm. 13C{1H} NMR
1
(s, 1 C, CH2), 33.1 (d, JCP = 53.1 Hz, 1 C, CH2), 35.9 (s, 1 C,
2
CH2), 39.6 (d, JCP = 2.5 Hz, 1 C, CH2), 109.5 (s, 1 C, =CH2),
2
123.6 (s, 1 C, Me2C=CH), 128.6 (d, JCP = 11.3 Hz, 2 C, o-Ph),
3
4
130.4 (d, JCP = 10.1 Hz, 2 C, m-Ph), 131.6 (d, JCP = 2.8 Hz, 1 C,
1
p-Ph), 132.1 [s, 1 C, =C(CH3)2], 132.2 (d, JCP = 80.3 Hz, 1 C,
ipso-Ph), 148.0 (d, JCP = 15.8 Hz, 1 C, =CCH3) ppm. C17H25PS
3
2
(CDCl3): δ = 25.6 (s, 1 C, CH3), 29.9 (d, JCP = 2.3 Hz, 1 C, CH2),
1
(292.42): calcd. C 69.82, H 8.62, S 10.97; found C 70.07, H 8.50, S
10.86.
30.9 (d, JCP = 56 Hz, 1 C, CH2), 110.3 (s, 1 C, =CH2), 128.7 (d,
3
2JCP = 11.3 Hz, 4 C, o-Ph), 131.1 (d, JCP = 9.8 Hz, 4 C, m-Ph),
131.5 (d, 4JCP = 3 Hz, 2 C, p-Ph), 133.4 (d, 1JCP = 80 Hz, 2 C, ipso-
Ph), 144.5 (d, 3JCP = 17 Hz, 1 C, C=CH2) ppm. C17H19PS (286.37):
calcd. C 71.30, H 6.69, S 11.20; found C 71.15, H 6.77, S 11.53.
[2-(6,6-Dimethylbicyclo[3.1.1]-2-heptenyl)ethyl]diphenylphosphane
Sulfide (1h): Colourless oil (398 mg, 87% yield). Rf = 0.5 (pentane/
Et2O, 9:1). 31P{1H} NMR (CDCl3): δ = 41.1 (s, PPh2) ppm. 1H
NMR (CDCl3): δ = 0.53 (s, 3 H, CH3), 1.16 (s, 3 H, CH3), 1.21
(m, 1 H, CH2), 1.73–1.78 (m, 2 H, CH2), 1.92 (m, 1 H, CH2), 2.10
(3-Methyl-3-butenyl)(methyl)phenylphosphane Sulfide (1b): Colour-
less oil (258 mg, 92% yield). Rf = 0.6 (pentane/Et2O, 9:1). 31P{1H}
3
1
(m, 1 H, CH), 2.15–2.35 (m, 2 H, CH2), 2.61 (t, JHH = 5.4 Hz, 1
NMR (CDCl3): δ = 39.7 (s, PMePh) ppm. H NMR (CDCl3): δ =
2
H, CH), 3.21 (td, 2JPH = 14.6, JHH = 7.2 Hz, 1 H, CH2), 3.35 (td,
2
1.71 (s, 3 H, CH3), 1.95 (d, JPH = 12.9 Hz, 3 H, CH3-P), 2.10 (m,
3
3
2JPH = 14.6, JHH = 8.2 Hz, 1 H, CH2), 5.12 (pseudo q, JHH
=
1 H, CH2), 2.18–2.28 (m, 2 H, CH2), 2.37 (m, 1 H, CH2), 4.69 (s,
1 H, =CH2), 4.73 (s, 1 H, =CH2), 7.45–7.60 (m, 3 H, Ph), 7.89–
3JPH = 7.5 Hz, 1 H, =CH), 7.40–7.51 (m, 6 H, Ph), 7.75–7.92 (m,
4 H, Ph) ppm. 13C{1H} NMR (CDCl3): δ = 19.0 (d, 5JCP = 2.3 Hz,
1 C, CH2), 20.9 (s, 1 C, CH3), 22.4 (s, 1 C, CH2), 24.9 (s, 1 C, CH3),
1
7.93 (m, 2 H, Ph) ppm. 13C{1H} NMR (CDCl3): δ = 20.8 (d, JCP
2
= 56.6 Hz, 1 C, PCH3), 22.5 (s, 1 C, CH3), 30.1 (d, JCP = 2.3 Hz,
2
1
1 C, CH2), 33.0 (d, 1JCP = 55.1 Hz, 1 C, CH2), 110.4 (s, 1 C, =CH2),
128.5 (d, 2JCP = 11.3 Hz, 4 C, o-Ph), 130.5 (d, 3JCP = 10.6 Hz, 4 C,
m-Ph), 131.6 (d, 4JCP = 3 Hz, 2 C, p-Ph), 132.2 (d, 1JCP = 77.7 Hz, 2
C, ipso-Ph), 144.3 (d, 3JCP = 15.8 Hz, 1 C, C=CH2) ppm. C12H17PS
(224.3): calcd. C 64.26, H 7.64, S 14.30; found C 64.64, H 7.81, S
14.62.
26.6 (d, JCP = 3.8 Hz, 1 C, CH2), 32.3 (d, JCP = 54.8 Hz, 1 C,
CH2), 39.5 (d, 5JCP = 4.5 Hz, 1 C, CH), 39.5 [s, 1 C, C(CH3)2], 51.6
(d, JCP = 2.3 Hz, 1 C, CH), 109.3 (d, JCP = 8.3 Hz, 1 C, =CH),
4
2
2
2
127.3 (d, JCP = 12 Hz, 2 C, o-Ph), 127.5 (d, JCP = 11.3 Hz, 2 C,
o-Ph), 130.1 (d, 3JCP = 9.8 Hz, 2 C, m-Ph), 130.3 (d, 4JCP = 3.8 Hz,
4
3
1 C, p-Ph), 130.4 (d, JCP = 3.8 Hz, 1 C, p-Ph), 130.5 (d, JCP
9.8 Hz, 2 C, m-Ph), 131.5 (d, JCP = 78.8 Hz, 1 C, ipso-Ph), 132.3
(d, JCP = 78.8 Hz, 1 C, ipso-Ph), 147.5 (d, JCP = 13.5 Hz, 1 C,
C=CH) ppm. C23H27PS (366.50): calcd. C 75.37, H 7.43, S 8.75;
found C 75.36, H 7.49, S 9.01.
=
1
(3-Methyl-3-butenyl)dicyclohexylphosphane Sulfide (1c): Colourless
oil (346 mg, 93% yield). Rf = 0.6 (pentane/Et2O, 9:1). 31P{1H}
NMR (CDCl3): δ = 58.8 (s, PCy2) ppm. 1H NMR (CDCl3): δ =
1.23–1.54 (m, 10 H, CH2), 1.78 (s, 3 H, CH3), 1.83–1.95 (m, 12 H,
1
3
CH2), 1.98–2.09 (m, 2 H, CH2), 2.27–2.38 (m, 2 H, CH2), 4.74 (s, (Cyclohex-3-enyl)diphenylphosphane Sulfide (1i): Colourless oil
1 H, C=CH2), 4.77 (s, 1 H, C=CH2) ppm. 13C{1H} NMR (CDCl3): (324 mg, 87% yield). Rf = 0.5 (pentane/Et2O, 9:1). 31P{1H} NMR
1
δ = 22.6 (s, 1 C, CH3), 24.0 (d, JCP = 46 Hz, 2 C, CH2), 25.9 (d,
4JCP = 1.5 Hz, 2 C, CH2), 26.1 (d, 3JCP = 3 Hz, 2 C, CH2), 26.3 (d,
3JCP = 3 Hz, 2 C, CH2), 26.5 (d, 2JCP = 3.8 Hz, 2 C, CH2), 26.7 (d,
(CDCl3): δ = 49.8 (s, PPh2) ppm. 1H NMR (CDCl3): δ = 1.70–1.91
(m, 3 H, CH2), 2.01–2.25 (m, 2 H, CH2), 2.49 (m, 1 H, CH2), 2.86
(m, 1 H, CH), 5.65–5.78 (m, 2 H, =CH), 7.43–7.54 (m, 6 H, Ph),
Eur. J. Org. Chem. 2010, 1562–1568
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A. Perrier, V. Comte, C. Moïse, P. Richard, P. Le Gendre
FULL PAPER
7.89–8.02 (m, 4 H, Ph) ppm. 13C{1H} NMR (CDCl3): δ = 21.8 (d,
(s, 1 C, p-Ph), 128.2 (s, 2 C, o-Ph), 128.7 (s, 2 C, m-Ph), 141.5 (s, 1
C, ipso-Ph) ppm.
JCP = 1.5 Hz, 1 C, CH2), 24.2 (s, 1 C, CH2), 25.0 (d, JCP = 14.3 Hz,
1
1 C, CH2), 34.2 (d, JCP = 58.1 Hz, 1 C, CH), 125.6 (d, JCP
=
(2,2-Diphenylethyl)diphenylphosphane Sulfide (5): White solid
(418 mg, 84% yield). Rf = 0.6 (pentane/Et2O, 9:1). 31P{1H} NMR
14.3 Hz, 1 C, =CH), 126.5 (d, JCP = 1.5 Hz, 1 C, =CH), 128.5 (d,
2
2JCP = 11.3 Hz, 2 C, o-Ph), 128.6 (d, JCP = 11.3 Hz, 2 C, o-Ph),
1
(CDCl3): δ = 41.8 (s, PPh2) ppm. H NMR (CDCl3): δ = 3.18 (dd,
1
4
130.9 (d, JCP = 77.7 Hz, 1 C, ipso-Ph), 131.3 (d, JCP = 4.5 Hz, 1
2JPH = 11.4, 3JHH = 6.9 Hz, 2 H, CH2), 4.86 (dt, 3JPH = 14.1, 3JHH
= 6.9 Hz, 1 H, CH), 7.01–7.88 (m, 20 H, Ph) ppm. 13C{1H} NMR
(CDCl3): δ = 38.6 (d, 1JCP = 55.8 Hz, 1 C, CH2), 45.1 (s, 1 C, CH),
C, p-Ph), 131.4 (d, 3JCP = 9 Hz, 2 C, m-Ph), 131.4 (d, 4JCP = 4.5 Hz,
1 C, p-Ph), 131.5 (d, JCP = 9 Hz, 2 C, m-Ph), 131.9 (d, JCP
3
1
=
77 Hz, 1 C, ipso-Ph) ppm. C18H19PS (298.38): calcd. C 72.45, H
6.42, S 10.75; found C 72.69, H 6.25, S 10.84.
2
126.4 (s, 2 C, p-Ph), 128.0 (s, 4 C, o-Ph), 128.2 (d, JCP = 12.8 Hz,
4
4 C, o-Ph), 128.3 (s, 4 C, m-Ph), 131.0 (d, JCP = 3 Hz, 2 C, p-Ph),
3
1
131.1 (d, JCP = 10.5 Hz, 4 C, m-Ph), 132.8 (d, JCP = 80.8 Hz, 2
(2,3-Dimethyl-2-butenyl)diphenylphosphane Sulfide (2f): Colourless
oil (334 mg, 89% yield). Rf = 0.6 (pentane/Et2O, 9:1). 31P{1H}
NMR (CDCl3): δ = 39.1 (s, PPh2) ppm. 1H NMR (CDCl3): δ =
1.35 [d, 5JPH = 4 Hz, 3 H, =C(CH3)2], 1.60 (m, 3 H, =CCH3), 1.63
3
C, ipso-Ph), 143.5 (d, JCP = 8 Hz, 2 C, ipso-Ph) ppm. C26H23PS
(398.5): calcd. C 78.36, H 5.82, S 8.05; found C 79.01, H 5.70, S
8.38.
5
2
[d, JPH = 6.4 Hz, 3 H, =C(CH3)2], 3.45 (d, JPH = 14.1 Hz, 2 H,
CH2), 7.42–7.55 (m, 6 H, Ph), 7.84–7.92 (m, 4 H, Ph) ppm.
(1-Methyl-1-phenylethyl)diphenylphosphane Sulfide (6): Colourless
oil (382 mg, 91% yield). Rf = 0.6 (pentane/Et2O, 9:1). 31P{1H}
NMR (CDCl3): δ = 55.5 (s, PPh2) ppm. 1H NMR (CDCl3): δ =
1.91 (s, 6 H, CH3), 7.01–7.14 (m, 3 H, Ph), 7.27–7.39 (m, 8 H, Ph),
7.78–7.88 (m, 4 H, Ph) ppm. 13C{1H} NMR (CDCl3): δ = 30.9 (s,
13C{1H} NMR (CDCl3): δ = 20.6 (d, JCP = 1.1 Hz, 1 C, =CCH3),
20.9 [d, JCP = 3.3 Hz, 1 C, =C(CH3)2], 21.2 [d, JCP = 3.3 Hz, 1
C, =C(CH3)2], 40.2 (d, JCP = 52.2 Hz, 1 C, CH2), 118.4 (d, JCP
= 10.4 Hz, 1 C, =CCH3), 128.4 (d, JCP = 11.7 Hz, 4 C, o-Ph),
131.3 (d, JCP = 2.7 Hz, 2 C, p-Ph), 131.4 [d, JCP = 12.1 Hz, 1 C,
=C(CH3)2], 131.5 (d, JCP = 9.7 Hz, 4 C, m-Ph), 133.4 (d, JCP
3
4
4
1
2
2
1
1 C, CH3), 31.0 (s, 1 C, CH3), 76.9 [d, JCP = 47.5 Hz, 1 C,
4
3
2
C(CH3)2], 126.4 (s, 2 C, o-Ph), 127.2 (s, 1 C, p-Ph), 128.1 (d, JCP
3
1
=
4
= 14.3 Hz, 4 C, o-Ph), 128.4 (s, 2 C, m-Ph), 131.4 (d, JCP = 3 Hz,
77.4 Hz, 2 C, ipso-Ph) ppm. C18H21PS (300.4): calcd. C 71.97, H
7.05, S 10.67; found C 71.95, H 7.26, S 10.93.
3
2 C, p-Ph), 131.6 (d, JCP = 11.3 Hz, 4 C, m-Ph), 134.4 (s, 1 C,
1
ipso-Ph), 134.9 (d, JCP = 80.8 Hz, 2 C, ipso-Ph) ppm. C21H21PS
(336.4): calcd. C 74.97, H 6.29, S 9.53; found C 75.12, H 6.29, S
9.85.
(2,3-Dimethyl-2-butenyl)(methyl)phenylphosphane Sulfide (2g):
Colourless oil (268 mg, 90% yield). Rf = 0.6 (pentane/Et2O, 9:1).
31P{1H} NMR (CDCl3): δ = 36.1 (s, PMePh) ppm. 1H NMR
Styryldiphenylphosphane Sulfide (7): White solid (380 mg, 95%
yield, Z/E: 60:40). Rf = 0.6 (pentane/Et2O, 9:1). C20H17PS (320.4):
calcd. C 74.98, H 5.35, S 10.01; found C 74.95, H 5.35, S 10.44.
(Z) isomer: 31P{1H} NMR (CDCl3): δ = 30.3 (s, PPh2) ppm. 1H
5
(CDCl3): δ = 1.46 [d, JPH = 3.4 Hz, 3 H, =C(CH3)2], 1.64 (m, 3
5
2
H, =CCH3), 1.66 [d, JPH = 5.2 Hz, 3 H, =C(CH3)2], 2.0 (d, JPH
2
2
= 12.8 Hz, 3 H, PCH3), 2.98 (pseudo t, JPH = JHH = 14.8 Hz, 1
H, CH2), 3.09 (pseudo t, 2JPH = 2JHH = 14.5 Hz, 1 H, CH2), 7.40–
2
3
NMR (CDCl3): δ = 6.25 (dd, JPH = 17.4, JHH = 13 Hz, 1 H,
=CH), 6.85–6.95 (m, 3 H, Ph), 7.13–7.20 (m, 6 H, Ph), 7.25 (d,
7.60 (m, 3 H, Ph), 7.80–7.92 (m, 2 H, Ph) ppm. 13C{1H} NMR
1
(CDCl3): δ = 20.1 (d, JCP = 55.8 Hz, 1 C, P-CH3), 20.7 (d, 3JCP
=
3JHH = 13 Hz, 1 H, =CH), 7.33–7.36 (m, 2 H, Ph), 7.70–7.75 (m,
4
1
4 H, Ph) ppm. 13C{1H} NMR (CDCl3): δ = 123.1 (d, JCP
=
1.4 Hz, 1 C, =CCH3), 20.8 [d, JCP = 3.6 Hz, 1 C, =C(CH3)2], 21.3
[d, JCP = 3.5 Hz, 1 C, =C(CH3)2], 43.5 (d, JCP = 50.1 Hz, 1 C,
CH2), 119.2 (d, JCP = 11.2 Hz, 1 C, =CCH3), 128.4 (d, JCP
4
1
2
81.4 Hz, 1 C, =CH), 127.6 (s, 2 C, Ph), 128.4 (d, JCP = 12 Hz, 4
C, o-Ph), 128.9 (d, JCP = 2.3 Hz, 2 C, p-Ph), 130.3 (s, 2 C, Ph),
2
2
4
=
3
3
11.7 Hz, 2 C, o-Ph), 130.7 (d, JCP = 9.9 Hz, 2 C, m-Ph), 130.8 [d,
131.2 (d, JCP = 10.5 Hz, 4 C, m-Ph), 131.3 (s, 1 C, Ph), 133.1 (d,
3JCP = 11.8 Hz, 1 C, =C(CH3)2], 131.4 (d, JCP = 3.0 Hz, 1 C, p-
4
1JCP = 85 Hz, 2 C, ipso-Ph), 134.5 (d, 3JCP = 6.8 Hz, 1 C, ipso-Ph),
Ph), 133.2 (d, 1JCP = 75.1 Hz, 1 C, ipso-Ph) ppm. C13H19PS (238.3):
146.6 (d, JCP = 2.3 Hz, 1 C, =CH) ppm. (E) isomer: 31P{1H}
2
NMR (CDCl3): δ = 37.2 (s, PPh2) ppm. 1H NMR (CDCl3): δ = (d,
1 H, =CH), 6.85–6.95 (m, 3 H, Ph), 7.15–7.25 (m, 6 H, Ph), 7.33–
calcd. C 65.51, H 8.04, S 13.45; found C 65.56, H 7.95, S 13.69.
(2-Phenylethyl)diphenylphosphane Sulfide (3): White solid (358 mg,
89% yield, m.p. 94 °C). Rf = 0.6 (pentane/Et2O, 9:1). 31P{1H}
NMR (CDCl3): δ = 41.9 (s, PPh2) ppm. 1H NMR (CDCl3): δ =
2.72–2.84 (m, 2 H, CH2), 2.80–3.10 (m, 2 H, CH2), 7.16–7.24 (m,
3 H, Ph), 7.25–7.32 (m, 2 H, Ph), 7.44–7.56 (m, 6 H, Ph), 7.84–
3
7.36 (m, 2 H, Ph), 7.51 (dd, JPH = 22.2, JHH = 16.3 Hz, 1 H,
=CH), 7.70–7.75 (m, 4 H, Ph) ppm. 13C{1H} NMR (CDCl3): δ =
119.9 (d, 1JCP = 86.7 Hz, 1 C, =CH), 127.9 (s, 1 C, p-Ph), 128.8 (d,
2JCP = 12 Hz, 4 C, o-Ph), 130.2 (d, 4JCP = 5.3 Hz, 2 C, o-Ph), 131.3
(s, 2 C, m-Ph), 131.5 (d, 3JCP = 10.5 Hz, 4 C, m-Ph), 131.6 (d, 4JCP
= 3 Hz, 2 C, p-Ph), 133.1 (d, 1JCP = 85 Hz, 2 C, ipso-Ph), 135.0 (d,
2
7.92 (m, 4 H, Ph) ppm. 13C{1H} NMR (CDCl3): δ = 28.4 (d, JCP
1
= 1.7 Hz, 1 C, CH2), 34.6 (d, JCP = 55.0 Hz, 1 C, CH2), 126.4 (s,
2
3JCP = 19.6 Hz, 1 C, ipso-Ph), 147.9 (d, JCP = 6 Hz, 1 C,
2 C, o-Ph), 128.2 (s, 2 C, m-Ph), 128.6 (s, 1 C, p-Ph), 128.7 (d, 2JCP
3
=CH) ppm.
= 12.3 Hz, 4 C, o-Ph), 128.77 (s, 1 C, ipso-Ph), 131.1 (d, JCP
=
4
10.2 Hz, 4 C, m-Ph), 131.5 (d, JCP = 2.7 Hz, 2 C, p-Ph), 132.6 (d,
1JCP = 80.0 Hz, 2 C, ipso-Ph) ppm. C20H19PS (322.4): calcd. C
74.51, H 5.94, S 9.95; found C 74.82, H 6.11, S 10.17.
(1,2-Diphenylvinyl)diphenylphosphane Sulfide (8): White solid
(460 mg, 93% yield, Z/E: 60:40). Rf = 0.6 (pentane/Et2O, 9:1).
C26H21PS (396.5): calcd. C 78.76, H 5.34, S 8.09; found C 79.02,
H 5.29, S 8.27. (Z) isomer: 31P{1H} NMR (CDCl3): δ = 36.3 (s,
(2-Phenylethyl)dicyclohexylphosphane Sulfide (4): Colourless oil
(283 mg, 75% yield). Rf = 0.5 (pentane/Et2O, 9:1). 31P{1H} NMR
(CDCl3): δ = 58.4 (s, PCy2) ppm. 1H NMR (CDCl3): δ = 1.17–1.46
(m, 10 H, CH2), 1.74–1.87 (m, 12 H, CH2), 1.93–1.97 (m, 2 H,
1
PPh2) ppm. H NMR (CDCl3): δ = 6.80–6.85 (m, 2 H, Ph), 6.91–
6.94 (m, 2 H, Ph), 7.03–7.24 (m, 6 H, Ph), 7.39–7.55 (m, 6 H, Ph),
3
7.67 (d, JPH = 26 Hz, 1 H, =CH), 7.75–7.85 (m, 4 H, Ph) ppm.
1
(E) isomer: 31P{1H} NMR (CDCl3): δ = 48.05 (s, PPh2) ppm. H
CH2), 2.97–3.01 (m, 2 H, CH2), 7.19–7.26 (m, 3 H, Ph), 7.30–7.37
NMR (CDCl3): δ = 6.97–7.05 (m, 2 H, Ph), 7.09–7.25 (m, 8 H,
Ph), 7.28 (s, 1 H, =CH), 7.35–7.45 (m, 2 H, Ph), 7.53–7.67 (m, 4
H, Ph), 7.76–7.83 (m, 4 H, Ph) ppm.
4
(m, 2 H, Ph) ppm. 13C{1H} NMR (CDCl3): δ = 25.9 (d, JCP
=
3
3
1.5 Hz, 2 C, CH2), 26.2 (d, JCP = 3 Hz, 2 C, CH2), 26.4 (d, JCP
= 3 Hz, 2 C, CH2), 26.6 (d, 2JCP = 3.8 Hz, 2 C, CH2), 26.7 (d, 2JCP
1
= 3.8 Hz, 2 C, CH2), 27.7 (d, JCP = 44.5 Hz, 2 C, CH2), 29.5 (d,
(3,5-Cycloheptadienyl)diphenylphosphane Sulfide (9): Colorless oil
(353 mg, 91% yield). Rf = 0.6 (pentane/Et2O, 9:1). 31P{1H} NMR
2JCP = 3 Hz, 1 C, CH2), 37.8 (d, JCP = 47.5 Hz, 1 C, CH), 126.4
1
1566
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 1562–1568

nBuLi-Mediated Hydrophosphination Reactions
Table 3. Crystal and structure refinement data for 1a, 7 and 9.
Compounds
1a
7
9
Empirical formula
Formula weight
Temperature [K]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
C17H19PS
286.36
115(2)
C20H17PS
320.38
115(2)
monoclinic
P21/n
14.7081(4)
6.5173(2)
17.5033(6)
C19H19P
278.31
115(2)
monoclinic
P21/n
10.1117(5)
9.8388(6)
15.1645(8)
triclinic
¯
P1
9.2124(3)
9.3719(2)
10.0851(3)
64.156(1)
89.701(1)
87.191(2)
782.57(4)
2
1.215
0.29
0.45ϫ0.30ϫ0.20
304
97.152(1)
91.134(3)
γ [°]
Volume [Å3]
Z
1664.76(9)
4
1.278
1508.38(14)
4
1.226
ρcalcd. [g/cm3]
µ [mm–1]
Size [mm3]
F(000)
0.28
0.17
0.37ϫ0.25ϫ0.10
672
0.15ϫ0.05ϫ0.02
592
λ [Å]
0.71073
0.65
–11ՆhՅ11
–12ՆkՅ12
–13ՆlՅ12
6644
0.71073
0.65
–18ՆhՅ19
–8ՆkՅ7
–22ՆlՅ22
6464
0.71073
0.65
–13ՆhՅ13
–12ՆkՅ12
–19ՆlՅ19
6114
sin(θ)/λmax [Å–1]
Index ranges
Reflections collected
Rint
0.016
0.026
0.047
Unique ref. [IՆ2σ(I)]
Data/restraints/parameters
R(F)[FՆ4σ(F)][a]
wR(F2) (all data)[b]
Goodness-of-fit[c] on F2
∆ρ [eÅ–3]
3097
3550/0/173
0.035
0.090
1.05
3009
3768/0/199
0.035
0.082
1.03
2615
3414/0/181
0.059
0.123
1.13
0.67 and –0.33
0.29 and –0.32
0.36 and –0.29
[a] R1 = Σ(||Fo| – |Fc||)/Σ|Fo|. [b] wR2 = [Σw(Fo – Fc ) /Σ[w(Fo2)2]½ in which w = 1/[σ2(Fo + (0.0369P)2 + 0.4348P)] for 1a, w = 1/[σ2(Fo
2
2 2
2
2
+ (0.0214P)2 + 0.8766P)] for 7 and w = 1/[σ2(Fo + (0.0P)2 + 2.3806P)] for 9 in which P = [Max(Fo2,0) + 2*Fc ]/3. [c] S = [Σw(Fo
Fc )(n – p)] (n = number of reflections, p = number of pmeters).
–
2
2
2
2
½
(CDCl3): δ = 50.9 (s, PPh2) ppm. 1H NMR (CDCl3): δ = 2.29–2.45
3
(m, 2 H, CH2), 2.55–2.71 (m, 2 H, CH2), 3.35 (dtt, JHH = 10.7,
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2JPH = 8, JHH = 2.3 Hz, 1 H, CH), 5.77–5.88 (m, 4 H, =CH),
3
7.40–7.55 (m, 6 H, Ph), 7.90–8.05 (m, 4 H, Ph) ppm. 13C{1H}
1
NMR (CDCl3): δ = 30.9 (s, 2 C, CH2), 35.9 (d, JCP = 53 Hz, 1 C,
CH), 125.7 (s, 2 C, =CH), 128.7 (d, 2JCP = 12 Hz, 4 C, o-Ph), 131.2
3
4
(d, JCP = 9.8 Hz, 4 C, m-Ph), 131.4 (d, JCP = 3 Hz, 2 C, p-Ph),
1
3
131.8 (d, JCP = 77.7 Hz, 2 C, ipso-Ph), 131.9 (d, JCP = 19.6 Hz,
1 C, =CH) ppm. C19H19PS (310.39): calcd. C 73.52, H 6.17, S
10.33; found C 73.45, H 6.38, S 10.57.
X-ray Analysis of Compounds 1a, 7 and 9: Intensity data were col-
lected at 115 K with a Nonius–Kappa instrument with an APEX
II detector. The structures were solved by direct methods
(SIR92)[17] and refined by full-matrix least-squares methods based
on F2 (SHELXL-97)[18] with the aid of the WINGX program.[19]
All non-hydrogen atoms were refined with anisotropic thermal pa-
rameters. Hydrogen atoms were included in their calculated posi-
tions and refined with a riding model. The crystallographic data
are reported in Table 3.
[2]
CCDC-739865 (for 1a), -739864 (for 7) and -739866 (for 9) contain
the supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
[3]
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Acknowledgments
This work was supported by the Agence Nationale de la Recherche
(ANR MetChirPhos).
Eur. J. Org. Chem. 2010, 1562–1568
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
1567

A. Perrier, V. Comte, C. Moïse, P. Richard, P. Le Gendre
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J. Seayad, A. Tillack, C. G. Hartung, M. Beller, Adv. Synth.
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The hydrophosphination of terminal and internal alkynes using
catalytic amounts of base has been studied in detail using other
systems: KOH/DMSO[10] and tBuOK/THF.[4d,4e]
[13]
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[15]
The addition of a stoichiometric amount of PPh2Li and phen-
ylacetylene followed by hydrolysis led to (E)-styrylphosphane
as the major isomer.[4a]
[16] Intermolecular hydrophosphination/polymerization from sec-
ondary phosphanes bearing alkyne substituents promoted by
nBuLi in THF has recently been reported: S. Greenberg, D. W.
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[17] A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, J.
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[18] G. M. Sheldrick, SHELXL-97, Program for the Refinement of
Crystal Structures, G. M. Sheldrick, University of Göttingen,
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[19] L. J. Farrugia, J. Appl. Crystallogr. 1999, 32, 837–838.
Received: December 3, 2009
Published Online: January 29, 2010
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