Stereoselective preparation of (Z)-α-stannyl-1-alkenyl sulfoxides via hydrozirconation of acetylenic stannanes

Article abstract of DOI:10.1016/S0022-328X(00)00129-7

Acetylenic stannanes (1) react with Cp₂Zr(H)Cl (Cp=η⁵-C₅H₅) giving (Z)-α-stannylvinylzirconium complexes (2), which are trapped with sulfinyl chlorides (3) in THF at room temperature to afford (Z)-α-stannyl-1-al

Full text of DOI:10.1016/S0022-328X(00)00129-7

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Journal of Organometallic Chemistry 603 (2000) 249–251
Note
Stereoselective preparation of (Z)-a-stannyl-1-alkenyl sulfoxides via
hydrozirconation of acetylenic stannanes
Xian Huang *, Ping Zhong, Meng-Ping Guo
Department of Chemistry, Zhejiang Uni6ersity, Xixi Campus, Hangzhou 310028, PR China
Received 30 November 1999; received in revised form 17 February 2000
Abstract
Acetylenic stannanes (1) react with Cp2Zr(H)Cl (Cp=h5-C5H5) giving (Z)-a-stannylvinylzirconium complexes (2), which are
trapped with sulfinyl chlorides (3) in THF at room temperature to afford (Z)-a-stannyl-1-alkenyl sulfoxides (4). The yields are
63–81%. The coupling of 4h with diphenyliodonium chloride in the presence of Pd(PPh3)4 and CuI afford (E)-a-phenyl
unsaturated sulfoxide 5 in 75% yield. © 2000 Published by Elsevier Science S.A. All rights reserved.
Keywords: Alkynylstannane; Organozirconocene compound; Hydrozirconation; Sulfinyl chloride; Sulfoxidation; (Z)-a-Stannyl-1-alkenyl sulfoxide
2. Results and discussion
1. Introduction
Alkynylstannanes (1) and sulfinyl chlorides (3) were
prepared according to the literature, respectively
[10,11]. Hydrozirconation of alkynylstannanes at room
temperature (r.t.) in THF gave (Z)-a-stannylvinylzirco-
nium complexes (2), which reacted with sulfinyl chlo-
rides to afford (Z)-a-stannyl substituted a,b-
unsaturated sulfoxides (4). The yields were 63–81%
(Scheme 1).
Alkenyl sulfoxides [1–3] and alkenyl stannanes [4]
have been used as synthetic intermediates to construct
some olefins. The reaction of 1-hexynyl-1-(4-
methylphenyl)sulfoxide with tributyltin hydride af-
forded a mixture of (E)-1-hexenyl-1-(4-methylphenyl)-
sulfinyl tributyl stannane and its (Z)-stereoisomer [5].
Herein, we want to find a convenient approach to
(Z)-1-hexenyl-1-(4-methylphenyl)sulfinyl tributyl stan-
nane from acetylenic stannanes. Hydrozirconation has
emerged as a unique hydrometallation with some at-
tractive features [6], such as the high regioselectivity
and stereoselectivity observed with alkynes [7]. How-
ever, to date, hydrozirconation of alkynylstannanes has
been receiving less attention [8,9]. Therefore, we now
wish to report that (Z)-a-stannyl substituted a,b-unsat-
urated sulfoxides could be synthesized by hydrozircona-
tion of the alkynylstannanes, followed by treatment
with sulfinyl chlorides, although the sulfoxidation of
vinylzirconium complexes has not been reported.
1
Investigations of the crude products 4 by H-NMR
spectroscopy (300 MHz) showed isomeric purities of
more than 96%. One olefinic proton signal of 4 was
characteristically split into one triplet with coupling
constant J=7.0 Hz, which indicated that the hydrozir-
conation of the alkynylstannes has a strong preference
for the addition of the zirconium atom at the carbon
adjacent to the alkylstannyl group. The results of the
reaction were summarized in Table 1.
* Corresponding author. Fax: +86-571-8807077.
E-mail address: xhuang@mail.hz.zj.cn (X. Huang)
Scheme 1.
0022-328X/00/$ - see front matter © 2000 Published by Elsevier Science S.A. All rights reserved.
PII: S0022-328X(00)00129-7

250
X. Huang et al. / Journal of Organometallic Chemistry 603 (2000) 249–251
Table 1
Synthesis of a-stannyl-a,b-unsaturated sulfoxides
a
Entry
R
R1
R2
Product
Yield b (%)
a
b
c
d
e
f
g
h
i
C6H5
C6H5 C6H5
C6H5 C6H5
C6H5 C6H5
4a
4b
4c
4d
80
75
81
68
77
70
79
65
63
69
nC5H11
nC4H9
Scheme 2.
CH3OCH2 C6H5 C6H5
C6H5
C6H5 p-MeC6H4 4e
C6H5 p-MeC6H4 4f
C6H5 p-MeC6H4 4g
C6H5 CH3
C6H5 CH3
nC5H11
nC4H9
C6H5
stirred at r.t. for about 2 h. The solvent was removed
by a rotary evaporator under reduced pressure. The
residue was extracted with a mixed solvent (ether–
EtOAc, 2:1) and filtered though a short plug of silica
gel. After the removal of the solvent, the oily residue
was purified by flash column chromatography silica gel
(1:10 EtOAc–hexane) to give 4a–j.
4h
4i
4j
nC4H9
j
CH3OCH2 nC4H9 C6H5
a All the compounds were characterized using 1H-NMR, IR, MS or
elemental analyses.
Characterisation data of 4a–g are as follows.
b Isolated yield based on the alkynylstannanes.
3.1.1. Compound 4a
Oil. 1H-NMR (CDCl3, l ppm): l=8.15–7.90 (m,
2H), 7.75–7.00 (m, 24H). IR w (cm−1): 3095, 1695,
1595, 1075. MS: m/z 578 [M+, 2.3], 351 (47.6), 154
(100%). Anal. Calc. for C32H26OSSn: C, 66.58; H, 4.54.
Found: C, 65.87; H, 4.61%.
We also tried to carry out the coupling reaction of
compound 4h at 0°C in CH2Cl2 with diphenyliodonium
chloride in the presence of Pd(PPh3)4 (0.1 equivalents)
and CuI (0.8 equivalents) for 2 h to give (E)-a-phenyl
unsaturated sulfoxide (5) [12] in 75% yield with high
stereroselectivity (Scheme 2).
In summary, our results showed that the hydrozir-
conation/sulfoxidation sequence of the alkynylstan-
nanes has advantages of readily available starting
materials, straightforward and simple procedures, mild
reaction conditions and high yields. The investigation
on the synthetic applications of these a-stannyl a,b-un-
saturated sulfoxides is in progress.
3.1.2. Compound 4b
Oil. 1H-NMR (CDCl3, l ppm): l=7.80–7.15 (m,
20H), 6.75 (t, J=7.3 Hz, 1H), 2,40–2.05 (m, 2H),
1.50–0.70 (m, 9H). IR w (cm−1): 3095, 1665, 1145,
1080, 1020. MS: m/z 572 [M+, 1.9], 515 (4.6), 351 (8.6),
154 (100%). Anal. Calc. for C31H32OSSn: C, 65.17; H,
5.65. Found: C, 65.38; H, 5.76%.
3.1.3. Compound 4c
Oil. 1H-NMR (CDCl3, l ppm): l=7.80–7.10 (m,
20H), 6.85 (t, J=7.3 Hz, 1H), 2.25–1.90 (m, 2H),
1.30–0.60 (m, 7H). IR w (cm−1): 3080, 1590, 1075,
1022. MS: m/z 558 [M+, 1.5], 515 (3.1), 351 (36.5), 154
(100%). Anal. Calc. for C30H30OSSn: C, 64.65; H, 5.42.
Found: C, 65.01; H, 5.66%.
3. Experimental
1H-NMR spectra were recorded on an AZ-300 MHz
spectrometer with TMS as an internal standard. Mass
spectra were determined using a Finigan 8230 mass
spectrometer. IR spectra were obtained by use of neat
capillary cells on a Shimadzu IR-408 instrument. Ele-
mental analyses were performed using a Carlo Erba
1106 analyzer. The reactions were carried out in pre-
dried (150°C, 4 h) glassware and cooled under a stream
of dry nitrogen. All solvents were dried, deoxygenated
and redistilled before use.
3.1.4. Compound 4d
Oil. 1H-NMR (CDCl3, l ppm): l=7.80–7.10 (m,
20H), 6.15 (t, J=7.5 Hz, 1H), 4.10 (d, J=7.5 Hz, 2H),
3.25 (s, 3H). IR w (cm−1): 3070, 1585, 1075, 1022. MS:
m/z 546 [M+, 1.1], 515 (6.4), 351 (28.6), 154 (100%).
Anal. Calc. for C28H26O2SSn: C, 61.68; H, 4.80. Found:
C, 61.49; H, 4.65%.
3.1. General procedure for the synthesis of
(Z)-h-stannyl-h,i-unsaturated sulfoxides (4a–j)
To a suspension of zirconocene hydrochloride (1.2
mmol) in THF (6 ml) was added a solution of the
alkynylstannanes (1.0 mmol) in THF at r.t. with stir-
ring. After 30 min of stirring, the reaction mixture
turned to a clear green solution, and the sulfinyl chlo-
ride (1.2 mmol) was added. The reaction mixture was
3.1.5. Compound 4e
Oil. 1H-NMR (CDCl3, l ppm): l=8.05–7.90 (m,
2H), 7.75–7.15 (m, 23H), 2.25 (s, 3H). IR w (cm−1):
3095, 1580, 1070, 1025. MS: m/z 592 [M+, 0.9], 351
(63), 154 (100%). Anal. Calc. for C33H28OSSn: C, 67.03;
H, 4.77. Found: C, 67.26%; H, 4.68%.

X. Huang et al. / Journal of Organometallic Chemistry 603 (2000) 249–251
251
3.1.6. Compound 4f
3.2. The synthesis of (E)-h-phenyl unsaturated
sulfoxide (5)
Oil. 1H-NMR (CDCl3, l ppm): l=7.80–7.20 (m,
19H), 6.73 ( t, J=7.0 Hz, 1H), 2.30 (s, 3H), 2.25–2.10
(m, 2H), 1.45–0.70 (m, 9H). IR w (cm−1): 3095, 1590,
1070, 1020. MS: m/z 586 [M+, 0.9], 529 (3.6), 351
(21.0), 77 (100%). Anal. Calc. for C32H34OSSn: C,
65.66; H, 5.85. Found: C, 64.78; H, 5.76%.
Compound 4h (0.5 mmol) and diphenyliodonium
chloride (0.5 mmol) were dissolved in CH2Cl2 (5 ml)
under nitrogen at 0°C. Pd(PPh3)4 (0.05 mmol) and CuI
(0.4 mmol) were then added. The mixture was stirred at
0°C and monitored by TLC for the disappearance of
the stating organostannane. The reaction mixture was
diluted with CH2Cl2 (15 ml), filtered and stirred with
20% aqueous KF (10 ml) for 30 min before being dried
and concentrated. The residue was purified by flash
column chromatography silica gel (1:10 EtOAc–hex-
ane) to give 5 in 75% yield.
3.1.7. Compound 4g
1
Oil. H-NMR ( CDCl3, l ppm): l=7.90–7.10 (m,
19H), 6.75(t, J=6 Hz, 1H), 2.35 (s, 3H), 2.25–1.95 (m,
2H), 1.50–0.80 (m, 7H). IR w (cm−1): 3080, 1595, 1075,
1040. MS: m/z 572 [M+, 1.8], 529 (3.6), 351 (21.3), 77
(100%). Anal. Calc. for C31H32OSSn: C, 65.17; H, 5.64.
Found: C, 65.39; H, 5.72%.
Acknowledgements
3.1.8. Compound 4h
Project 29772007 was supported by the National
Nature Science Foundation of China. This work was
also supported by the Laboratory of Organometallic
Chemistry, Chinese Academy of Science.
1
Oil. H-NMR ( CDCl3, l ppm): l=8.10–7.20 (m,
21H), 2.70 (s, 3H). IR w (cm−1): 3090, 1590, 1070,
1022. MS: m/z 516 [M+, 2.7], 351 (71), 154 (100%).
Anal. Calc. for C27H24OSSn: C, 62.94; H, 4.69. Found:
C, 63.83; H, 4.78%.
References
3.1.9. Compound 4i
Oil. H-NMR ( CDCl3, l ppm): l=7.80–7.10 (m,
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15H), 6.80 (t, J=7.0 Hz, 1H), 2.60 (s, 3H), 2.25–1.97
(m, 2H), 1.80–0.80 (m, 7H). IR w (cm−1): 3090, 1595,
1075, 1025. MS: m/z 496 [M+, 2.8], 453 (4.4), 351
(11.2), 77 (100%). Anal. Calc. for C25H28OSSn: C,
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3.1.10. Compound 4j
Oil. H-NMR ( CDCl3, l ppm): l=7.70–7.20 (m,
1
5H), 6.40 (t, J=7.0 Hz, 1H), 4.05 (d, 2H), 3.30 (s, 3H),
1.80–0.80 (m, 27H). IR w (cm−1): 3080, 2970, 2930,
1590, 1075, 1020. MS: m/z 486 [M+, 0.32], 455 (4.3),
291 (31.0), 45 (100%). Anal. Calc. for C22H38O2SSn: C,
54.45; H, 7.89. Found: C, 54.66; H, 7.86%.
.