Cis-carbocupration of acetylenic phosphine oxides and its application in the stereoselective synthesis of polysubstituted vinyl phosphine oxides

Article abstract of DOI:10.1055/s-2004-831222

Bisubstituted or 1,2,2-trisubstituted vinyl phosphine oxides were prepared stereoselectively by the carbocupration of acetylenic phosphine oxides followed by hydrolysis or by reacting with other electrophiles.

Full text of DOI:10.1055/s-2004-831222

PAPER
2445
Cis-Carbocupration of Acetylenic Phosphine Oxides and Its Application in the
Stereoselective Synthesis of Polysubstituted Vinyl Phosphine Oxides
C
is-Carbocupratio
i
n
of
A
c
a
etylenic
P
h
n
osphine
O
xides Huang,*a,b Zhimeng Wua
a
Department of Chemistry, Zhejiang University, Xixi Campus, Hangzhou 310028, P. R. China
b
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai,
200032, P. R. China
Fax +86(571)88807077; E-mail: huangx@mail.hz.zj.cn
Received 12 May 2004; revised 29 June 2004
action with acetylenic compounds.14 However, the Mi-
chael reaction of organocopper(I) reagents with 1-alkynyl
phosphine oxides has been observed in a few cases.15
Thus, as an extension of our study on the stereoselective
synthesis of functionalized alkenes, we report herein a
synthetic route for the preparation of polysubstituted vinyl
phosphine oxides by the Michael addition of organocop-
per(I) reagents to 1-alkynyl phosphine oxides.
Abstract: Bisubstituted or 1,2,2-trisubstituted vinyl phosphine ox-
ides were prepared stereoselectively by the carbocupration of acet-
ylenic phosphine oxides followed by hydrolysis or by reacting with
other electrophiles.
Keywords: carbocupration, acetylenic phosphine oxide, polysub-
stituted vinyl phosphine oxides
Preliminary experiments involved the treatment of 1-
alkynyl phosphine oxides16 with organocopper(I) re-
agents, prepared in situ from CuI and 2.0 equivalents of
alkylmagnesium bromide,17 followed by protolysis with
saturated ammonium chloride solution (Scheme 1). The
results are summarized in Table 1.
The synthesis of stereospecifically substituted alkenes is
one of the major challenges in organic synthesis, and is
still being actively explored because of the fact that many
biologically active compounds have the structure of sub-
stituted alkenes.1
We have prepared several kinds of functionalized vinyl
compounds by hydrozirconation,2a hydrotelluration,2b
carbomagnesiation,3 and selenomagnesiation4 of 1-alky-
nyl sulfones to afford stereodefined polysubstituted al-
kenes.
As indicated in Table 1, the reaction proceeds smoothly
with dialkyl or diaryl cuprates at –78 °C in THF. In all
cases, organocopper(I) reagents attack b-position of 1-
alkynyl phosphine oxides exclusively without side reac-
tion. The regioselectivity can be rationalized in terms of a
carbanion stabilization by the phosphine oxide. It was
found that a cis-addition happened when acetylenic phos-
phine oxides react with organocopper(I) reagents. The Z-
configuration of 3c was confirmed by NOE spectrum,
Unsaturated phosphorus compounds are interesting com-
pounds owing to their synthetic utility5 and biological ac-
tivity.6 On the other hand, vinyl phosphine oxides are
useful synthetic intermediate for nucleophile addition7
and cycloaddition reactions.8 Also some derivatives of vi-
nyl phosphine oxides can be used as biologically active
compounds.9 The available methodology for the stereo-
synthesis of substituted vinyl phosphine oxides mainly
consists of hydrogen-lithium exchange reaction of vinyl
phosphine oxides having no allylic hydrogen and subse-
quent treatment with various electrophiles,10 using phos-
phonium diylides reaction with aldehydes,11 vinyl
Grignard reagent reaction with diphenylchlorophosphine
and subsequently H2O2 oxidation,12 olefin cross-metathe-
sis using Grubbs and Hoveyda-type ruthenium catalysts.13
The chemistry of organocopper(I) reagents has received a
great deal of attention regarding cis-conjugate addition re-
Table 1 Organcopper(I) React with 1-Alkynyl Phosphine Oxides
(Electrophile = H+)
Entry
R1
R
Product Yield (%)a 3b
1
2
3
4
Ph
Et
Et
Me
Ph
3a
3b
3c
3d
85
80
79
82
only 3a
only 3b
only 3c
only 3d
MeOCH2
MeOCH2
C4H9
a Isolated yield based on 1.
b Other isomers were not detected in NMR studies.
R1
P(O)Ph2
R1
P(O)Ph2
H3O+
R2CuMgBr
R1
P(O)Ph2
R
R
H
RCuMgBr
3
2
1
Scheme 1
SYNTHESIS 2004, No. 15, pp 2445–2448
x
x.
x
x
.
2
0
0
4
Advanced online publication: 16.09.2004
DOI: 10.1055/s-2004-831222; Art ID: F06604SS
© Georg Thieme Verlag Stuttgart · New York

2446
X. Huang, Z. Wua
PAPER
R1
R
P(O)Ph2
R1
R
P(O)Ph2
E
R2CuMgBr
EX
R1
P(O)Ph2
RCuMgBr
1
4
2
Br
EX = I2, PhSeBr, PhTeI,
Scheme 2
which shows the correlation between the vinylic proton a-Iodinevinylphosphine oxides 4a, 4b were obtained by
and the protons of methyl group, while there is no correc- treating the intermediate 2 with iodine. When phenylsele-
tion between the vinylic proton and the methylene group. nyl bromide or phenyltelluryl iodine was used as electro-
phile, a-phenylchalcogenovinyl phosphine oxides 4c, 4d
The vinylcopper(I) species 2 are very important interme-
diates because they can react with a range of electrophiles
to give the a-functionalized vinyl phosphine oxides and
high retention of configuration. So we further investigated
and 4e were formed. Allylation products 4f and 4g were
also obtained with allyl bromide in good yields. However,
attempts of acylation of the vinylcopper(I) intermediates
with acetyl chloride and benzoyl chloride failed. The ste-
reochemistry of the reaction was verified by NOESY
the reaction of intermediate 2 with several electrophiles
having transmetalation properties (I, Se, Te)
spectra of compound 4f and the X-ray structure of com-
(Scheme 2).18 Results are summarized in Table 2.
pound 4g (Figure 1). The NOESY spectra of compound 4f
show that there is strong correlation between the allylic
protons of the allyl group and the ethyl group, while no
correlation was found between the allylic proton of the al-
lyl group and the n-butyl group. From Figure 1, we can
see that the ethyl group is cis oriented with respect to the
allyl group. These results show that the reaction occurred
in the cis-fashion.
In conclusion, the carbocupration of 1-alkynyl phosphine
oxides and further reaction with eletrophiles provide an
efficient way to synthesize polysubstituted vinyl phos-
phine oxides regio- and stereoselectively in a one pot pro-
cess. The reactions of intermediate 2 with other
electrophiles to synthesize various substituted vinyl phos-
phine oxides are now carried out in our laboratory.
1
All H NMR spectra were measured in CDCl3 and recorded on
Bruker Avance-400 (100 MHz) spectrometer with TMS as the in-
ternal standard. Chemical shifts are expressed in ppm and J values
are given in Hz. IR spectra were run on a Bruker vector 22 spec-
trometer. EIMS were determined with a HP5989B mass spectro-
meter. Elemental analyses were performed on an EA-1110
instrument. Melting points are uncorrected.
Figure 1 The molecular structure of 4g
Synthesis of 3a–3d; General Procedure
Table 2 Organcopper(I) React with 1-Alkynyl Phosphine Oxide
(Electrophile = E+)
CuI (142.5 mg, 0.75 mmol) was introduced into a stirred solution of
Grignard reagent (1.5 mmol) in THF (3 mL) at 0 °C. After stirring
for 15 min, the temperature was lowered to –78 °C. 1-Acetylenic
phosphine oxides (0.5 mmol) in THF (3 mL) were added slowly and
the reaction mixture was allowed to warm to –10 °C during several
hours, followed by protolysis with sat. aq NH4Cl (5 mL), then ex-
tracted with Et2O (3 ´ 15 mL), dried with Mg2SO4. After filtration
and removal of the solvent in vacuo, the crude product was purified
with flash chromatography (hexane–EtOAc, 1:1) to afford com-
pounds 3a–3d.
Entry
R1
R
E+
Product Yield (%)a
1
2
3
4
5
6
7
Ph
n-Bu
Et
I
4a
4b
4c
4d
4e
4f
85
79
81
80
74
80
75
MeOCH2
Ph
I
Et
PhSe
PhTe
PhTe
Ph
Et
MeOCH2
n-Bu
Ph
Ph
Et
3a
Oil.
Br
Br
IR (neat): 1600, 1441, 1176 cm–1.
Et
4g
1H NMR (400 MHz, CDCl3): d = 7.62–7.57 (m, 4 H), 7.33–7.25 (m,
6 H), 7.18–7.16 (m, 2 H), 7.06–7.04 (m, 3 H), 6.29 (d, J = 28.0 Hz,
1 H), 2.63 (q, J = 8.0 Hz, 2 H), 1.09 (t, J = 8.0 Hz, 3 H).
a Isolated yield based on 1.
Synthesis 2004, No. 15, 2445–2448 © Thieme Stuttgart · New York

PAPER
Cis-Carbocupration of Acetylenic Phosphine Oxides
2447
13C NMR (100 MHz, CDCl3): d = 166.59, 139.22 (d, J = 7.7 Hz),
134.52 (d, J = 104.1 Hz), 130.95, 130.84 (d, J = 9.2 Hz), 128.27 (d,
J = 11.4 Hz), 128.13, 128.06, 127.69, 118.64 (d, J = 105.2 Hz),
34.78 (d, J = 10.4 Hz), 12.54.
mmol; prepared by reaction of diphenyl ditelluride (0.5 mmol, 204
mg) with iodine (0.5 mmol, 127 mg) in THF (3 mL) for 1 h at r.t.];
in the case of 4f, 4g, ally bromide (1 mmol, 121 mg) in THF (2 mL)}
were added dropwise. The reaction mixtures were allowed to warm
to r.t. and quenched with aq NH4Cl (5 mL), then extracted with Et2O
(3 × 15 mL), and dried with Mg2SO4. After filtration and removal
of the solvent in vacuo, the crude product was purified with flash
chromatography (hexane–EtOAc, 1:1) to afford compounds 4a–4g.
MS (EI): m/z (%) = 333 (100) [M+ + 1].
Anal. Calcd for C22H21OP: C, 79.50; H, 6.37. Found: C, 79.62; H,
6.30.
3b
Oil.
4a
Oil.
IR (neat): 1580, 1445, 1170 cm–1.
IR (neat): 1603, 1448, 1183 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.76–7.71 (m, 4 H), 7.49–7.43 (m,
6 H), 6.05 (d, J = 36 Hz, 1 H), 4.40 (s, 2 H), 3.14 (s, 3 H), 2.38 (q,
J = 8.0 Hz, 2 H), 1.12 (t, J = 8.0 Hz, 3 H).
1H NMR (400 MHz, CDCl3): d = 7.74–7.65 (m, 4 H), 7.37–7.32 (m,
6 H), 7.13–7.08 (m, 5 H), 2.92 (t, J = 8 Hz, 2 H), 1.38–1.36 (m, 4
H), 0.86 (t, J = 8 Hz, 3 H).
13C NMR (100 MHz, CDCl3): d = 162.5, 134.80 (d, J = 104.2 Hz),
131.40 (d, J = 2.4 Hz), 130.60 (d, J = 9.5 Hz), 128.60 (d, J = 12.0
Hz), 119.70 (d, J = 101.5 Hz), 72.5 (d, J = 7.6 Hz), 51.3, 35.2 (d,
J = 10.3 Hz), 12.63.
13C NMR (100 MHz, CDCl3): d = 167.79 (d, J = 5.7 Hz), 139.25 (d,
J = 2.7 Hz), 132.37 (d, J = 108.5 Hz), 131.96 (d, J = 9.3 Hz), 131.30
(d, J = 2.7 Hz), 128.22 (d, J = 12.3 Hz), 128.04, 127.95, 127.72,
97.70 (d, J = 90 Hz), 49.27 (d, J = 9.1 Hz), 28.85, 22.61, 13. 9.
MS (EI): m/z (%) = 301 (100) [M+ + 1].
MS (EI): m/z (%) = 487 (100) [M+ + 1].
Anal. Calcd for C18H21O2P: C, 71.98; H, 7.05. Found: C, 71.83; H,
7.13.
Anal. Calcd for C24H24IOP: C, 59.27; H, 4.97. Found: C, 59.35; H,
4.82.
3c
Oil.
4b
Oil.
IR (neat): 1590, 1441, 1176 cm–1.
IR (neat): 1605, 1450, 1176 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.71–7.66 (m, 4 H), 7.44–7.40 (m,
6 H), 6.00 (d, J = 24.36 Hz, 1 H), 4.34 (s, 2 H), 3.11 (s, 3 H), 2.00
(s, 3 H).
1H NMR (400 MHz, CDCl3): d = 7.72–7.68 (m, 4 H), 7.47–7.43 (m,
6 H), 4.37 (s, 2 H), 3.12 (s, 3 H), 2.35 (q, J = 8.0 Hz, 2 H), 1.18 (t,
J = 8.0 Hz, 3 H).
13C NMR (100 MHz, CDCl3) d = 160.03, 134.95 (d, J = 104.1 Hz),
131.54 (d, J = 2.6 Hz), 130.86 (d, J = 9.7 Hz), 128.54 (d, J = 11.9
Hz), 119.49 (d, J = 101.7 Hz), 71.82 (d, J = 7.8 Hz), 51.15, 23.50
(d, J = 16.8 Hz).
13C NMR (100 MHz, CDCl3): d = 167.88 (d, J = 5.4 Hz), 132.82 (d,
J = 108.9 Hz), 132.46 (d, J = 9.3 Hz), 132.12 (d, J = 2.9 Hz), 128.38
(d, J = 12.8 Hz), 95.42 (d, J = 88.7), 70.41 (d, J = 6.6 Hz), 58.15,
36.35 (d, J = 9.6 Hz), 11.53.
MS (EI): m/z (%) = 287 (100) [M+ + 1].
Anal. Calcd for C18H20IO2P: C, 50.72; H, 4.73; Found: C, 50.69; H,
4.82.
Anal. Calcd for C17H19O2P: C, 71.32; H, 6.69. Found: C, 71.41; H,
6.58.
4c
Oil.
3d
IR (neat): 1586, 1441, 1173 cm–1.
Solid; mp 108–110 °C.
IR (KBr): 1599, 1440, 1176 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.74–7.65 (m, 4 H), 7.37–7.32 (m,
6 H), 7.13–7.08 (m, 5 H), 5.98 (d, J = 29 Hz, 1 H), 2.92 (t, J = 7.6
Hz, 2 H), 1.38–1.36 (m, 4 H), 0.86 (t, J = 7.6 Hz, 3 H).
1H NMR (400 MHz, CDCl3): d = 7.94–7.90 (m, 4 H), 7.50–7.47 (m,
3 H), 7.45–7.40 (m, 3 H), 7.14–7.10 (m, 3 H), 7.05–7.00 (m, 3 H),
6.98–6.94 (m, 2 H), 6.92–6.85 (m, 2 H), 2.46 (q, J = 8.0 Hz, 2 H),
0.95 (t, J = 8.0 Hz, 3 H).
13C NMR (100 MHz, CDCl3): d = 174.40 (d, J = 4.8 Hz), 143.40 (d,
J = 7.8 Hz), 138.5, 133.60 (d, J = 106.1 Hz), 132.10 (d, J = 9.2 Hz),
131.48 (d, J = 2.6 Hz), 130.5, 129.34 (d, J = 11.8 Hz), 128.80,
127.94, 127.83, 127.20, 126.16, 119.89 (d, J = 88.4 Hz), 32.79 (d,
J = 10.0 Hz), 12.53.
13C NMR (100 MHz, CDCl3): d = 164.95 (d, J = 2.9 Hz), 141.66 (d,
J = 17.3 Hz), 135.19 (d, J = 103.9 Hz), 131.51 (d, J = 3.0 Hz),
131.05 (d, J = 9.2 Hz), 128.95, 128.63 (d, J = 12.0 Hz), 128.61,
126.54, 119.15 (d, J = 104.3 Hz), 32.66 (d, J = 5.8 Hz), 30.77, 22.68,
13.80.
MS (EI): m/z (%) = 488 (100) [M+ + 1].
MS (EI): m/z (%) = 361 (100) [M+ + 1].
Anal. Calcd for C28H25OPSe: C, 68.99; H, 5.17. Found: C, 68.89; H,
5.28.
Anal. Calcd for C24H25OP: C, 79.98; H, 6.99. Found: C, 79.86; H,
7.01.
4d
Oil.
Synthesis of 4a–4g; General Procedure
CuI (142.5 mg, 0.75 mmol) was introduced into a stirred solution of
Grignard reagent (1.5 mmol) in THF (3 mL) at 0 °C. After stirring
for 15 min, the temperature was lowered to –78 °C. 1-Acetylenic
phosphine oxides (0.5 mmol) in THF (3 mL) were added slowly and
the reaction mixture was allowed to warm to –10 °C during several
hours. Then the reaction was again cooled to –78 °C and several
electrophiles {in the cases of 4a, 4b, iodine (0.5 mmol, 127 mg) in
THF (3 mL); in the case of 4c, phenyl selenyl bromide (1 mmol, 236
mg) in THF (3 mL); in case of 4d, 4e, phenyltelluryl iodine [1
IR (neat): 1631, 1445, 1176 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.96–7.90 (m, 4 H), 7.80–7.62 (m,
3 H), 7.56–7.38 (m, 3 H), 7.29–7.15 (m, 3 H), 7.10–7.00 (m, 3 H),
6.96–6.92 (m, 2 H), 6.90–6.85 (m, 2 H), 2.58 (q, J = 8.0 Hz, 2 H),
0.97 (t, J = 8.0 Hz, 3 H).
13C NMR (100 MHz, CDCl3): d = 172.15 (d, J = 4.7 Hz), 139.82 (d,
J = 7.8 Hz), 137.6, 134.99 (d, J = 104.6 Hz), 131.12 (d, J = 8.9 Hz),
Synthesis 2004, No. 15, 2445–2448 © Thieme Stuttgart · New York

2448
X. Huang, Z. Wua
PAPER
130.70 (d, J = 3.7 Hz), 129.47, 128.06 (d, J = 12.0 Hz), 127.96,
127.82, 127.73, 126.69, 118.54, 115.06 (d, J = 83.7 Hz), 41.98 (d,
J = 12.0 Hz), 11.57.
MS (EI): m/z (%) = 537 (100) [M+ + 1].
Acknowledgment
This work supported by the National Nature Science Foundation of
China (Project No. 20332060, 20272050).
Anal. Calcd for C28H25OPTe: C, 62.73; H, 4.70. Found: C, 62.82; H,
4.56.
References
(1) (a) Huang, X.; Sun, A. M. J. Org. Chem. 2000, 65, 6561.
(b) Wei, H. X.; Kim, S. H.; Caputo, T. D.; Purkiss, D. W.;
Li, G. G. Tetrahedron 2000, 56, 2397.
(2) (a) Huang, X.; Duan, D. H. Chem. Commun. 1999, 1741.
(b) Huang, X.; Liang, C. G.; Xu, Q.; He, Q. W. J. Org. Chem.
2001, 66, 74.
4e
Oil.
IR (neat): 1600, 1435, 1172 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.90–7.88 (m, 4 H), 7.52–7.47 (m,
3 H), 7.46–7.40 (m, 3 H), 7.14–7.12 (m, 3 H), 7.05–7.03 (m, 3 H),
6.98–6.96 (m, 2 H), 6.90–6.87 (m, 2 H), 4.53 (s, 2 H), 2.88 (s, 3 H).
(3) Xie, M. H.; Huang, X. Synlett 2003, 477.
(4) (a) Huang, X.; Xie, M. H. Org. Lett. 2002, 4, 1331.
(b) Huang, X.; Xie, M. H. J. Org. Chem. 2002, 67, 8895.
(5) (a) Han, L. B.; Zhao, C. Q.; Tanaka, M. J. Org. Chem. 2001,
66, 5929. (b) Minami, T.; Okauchi, T.; Kouno, R. Synthesis
2001, 349. (c) Clayden, J.; Warren, S. Angew. Chem., Int.
Ed. Engl. 1996, 35, 241. (d) Minami, T.; Motoyoshiya, J.
Synthesis 1992, 333. (e) Huang, X.; Zhang, C.; Lu, X.
Synthesis 1995, 769.
(6) (a) Engel, R. Chem. Rev. 1977, 77, 49. (b) Breaker, R. R.;
Gough, G. R.; Gilham, P. T. Biochemistry 1993, 32, 9125.
(7) (a) Bardels, B.; Clayden, J.; Martin, C. G.; Neslson, A.;
Russel, M. G.; Warren, S. J. Chem. Soc., Perkin Trans. 1
1999, 1807. (b) Clayden, J.; Neslson, A.; Warren, S.
Tetrahedron Lett. 1997, 38, 3471.
13C NMR (100 MHz, CDCl3): d = 168.40 (d, J = 4.8 Hz), 139.37 (d,
J = 8.0 Hz), 134.40 (d, J = 105.4 Hz), 131.77 (d, J = 2.0 Hz), 131.09
(d, J = 9.0 Hz), 129.41, 127.85, 127.67, 128.80, 127.64 (d, J = 11.8
Hz), 126.05, 125.67, 125.13, 118.04 (d, J = 88.4 Hz), 69.49 (d, J =
7.4 Hz), 58.13.
MS (EI): m/z (%) = 555 (100) [M+ + 1].
Anal. Calcd for C28H25O2PTe: C, 60.92; H, 4.56. Found: C, 60.86;
H, 4.63.
4f
Oil.
IR (neat): 1580, 1420, 1180 cm–1.
(8) (a) Brandi, A.; Cannaro, P.; Pietrusiewicz, K. M.; Zablocka,
M.; Wieczorek, M. J. Org. Chem. 1989, 54, 3073.
(b) Brandi, A.; Cicchi, S.; Goti, A. J. Org. Chem. 1991, 56,
4383.
(9) Nicolaou, K. C.; Maligres, P.; Shin, J.; deLeon, E.; Rideout,
D. J. Am. Chem. Soc. 1990, 112, 7825.
1H NMR (400 MHz, CDCl3): d = 7.70–7.67 (m, 4 H), 7.50–7.39 (m,
6 H), 5.48–5.44 (m, 1 H), 4.84 (dd, J = 10.0 Hz, J = 1.6 Hz, 2 H),
2.88 (q, J = 7.6 Hz, 2 H), 2.47 (t, J = 8.0 Hz, 2 H), 2.27 (q, J = 7.6
Hz, 3 H), 1.40–1.31 (m, 4 H), 1.12 (t, J = 7.3 Hz, 2 H), 0.74 (t, J =
6.9 Hz, 3 H).
13C NMR (100 MHz, CDCl3): d = 163.90 (d, J = 8.2 Hz), 135.17,
134.49 (d, J = 99.0 Hz), 131.77 (d, J = 9.1 Hz), 131.18 (d, J = 2.2
Hz), 128.11 (d, J = 12.1 Hz), 123.09 (d, J = 107.7 Hz), 115.74, 34.25
(d, J = 7.8 Hz), 34.13, 26.12 (d, J = 13.4 Hz), 22.89, 13.77, 12.76.
(10) Bartels, B.; Martin, C. G.; Nelson, A.; Russell, M. G.;
Warren, S. Tetrahedron Lett. 1998, 39, 1637.
(11) Taillefer, M.; Cristau, H. J. Tetrahedron Lett. 1998, 39, 857.
(12) (a) Robert, R.; Joseph, P. J. Org. Chem. 1961, 26, 4623.
(b) Berlin, K. D.; Butler, G. B. J. Org. Chem. 1961, 26, 2537.
(13) Demchuk, O. M.; Pietrusiewicz, K. M.; Michrowska, A.;
Grela, K. Org. Lett. 2003, 5, 3217.
(14) (a) Corey, E. J.; Katzenellenbogen, J. A. J. Am. Chem. Soc.
1969, 91, 1851. (b) Fiandanese, V.; Marchese, G.; Naso, F.
Tetrahedron Lett. 1978, 5131.
MS (EI): m/z (%) = 353 (100) [M+ + 1].
Anal. Calcd for C23H29OP: C, 78.38; H, 8.29. Found: C, 78.46; H,
8.17.
4g
Solid: mp 116–118 °C.
IR (KBr): 1600, 1425, 1165 cm–1.
(15) Adam, M. A.; Smiley Irelan, J. R. J. Org. Chem. 1969, 34,
4030.
1H NMR (400 MHz, CDCl3): d = 7.60–7.45 (m, 4 H), 7.27–7.7.18
(m, 6 H), 6.94–6.88 (m, 5 H), 5.67–5.63 (m, 1 H), 4.99–4.93 (m, 2
H), 3.10 (dd, J = 10.0 Hz, J = 1.6 Hz, 2 H), 2.50 (q, J = 8.0 Hz, 2
H), 0.95 (t, J = 8.0 Hz, 3 H).
13C NMR (100 MHz, CDCl3): d = 161.65 (d, J = 8.2 Hz), 140.07 (d,
J = 8.4 Hz), 136.53 (d, J = 1.6 Hz), 134.00 (d, J = 101.2 Hz), 131.45
(d, J = 10.2 Hz), 130.67 (d, J = 2.8 Hz), 129.17, 129.16, 127.80 (d,
J = 11.8 Hz), 127.1, 127.00, 115.97, 34.55 (d, J = 13.1 Hz), 30.45
(d, J = 12.5 Hz), 12.05.
(16) Charrier, C.; Chodkiewicz, W.; Cadiot, P. Bull. Soc. Chim.
Fr. 1966, 1002.
(17) (a) Normant, J. F. Synthesis 1972, 63. (b) Normant, J. F.;
Alexakis, A. Synthesis 1981, 841.
(18) For reviews on vinylic selenides and tellurides-preparation,
reactivity, and their synthetic application, see: Comasseto, J.
V.; Ling, L. W.; Petragnani, N.; Stefani, H. A. Synthesis
1997, 373.
(19) Crystal Data for 4g: C25H25OP, MW = 372.45, monoclinic,
space group, P21/n, a = 19.002(4), b = 6.305(2), c =
18.514(6) Å, b = 110.66(2)o, V = 2075(1) Å3, T = 293K, Z =
4, Dc = 1.92 g·cm–1, m = 1.44 mm–1, l = 0.71069 Å, F(000) =
792.00, independent reflections (Rint = 0.000), 8478
reflections collected; refinement method, full-matrix least-
squares refinement on F2; goodness-of-fit on F2 = 0.223;
Final R indices [ I > 2 s (I)] R1 = 0.050, wR2 = 0.094.
MS (EI): m/z (%) = 373 (100) [M+ + 1].
Anal. Calcd for C25H25OP: C, 80.62; H, 6.77. Found: C, 80.50; H,
6.82.
Synthesis 2004, No. 15, 2445–2448 © Thieme Stuttgart · New York