Preparation of α-heteroatom substituted allylic alcohols by reaction of (E)-α-selanylvinylzirconiums or (E)-α-trimethylsilylvinylzirconiums with aldehydes

Article abstract of DOI:10.1039/a900134d

Both (E)-α-selanylvinylzirconium and (E)-α- trimethylsilylvinylzirconium complexes undergo AgClO₄-catalyzed reactions with aldehydes to give α-seleno- or α-trimethylsilyl-substituted allylic alcohols, respectively.

Full text of DOI:10.1039/a900134d

View Article Online / Journal Homepage / Table of Contents for this issue
292 J. CHEM. RESEARCH (S), 1999
J. Chem. Research (S),
1999, 292^293y
Preparation of a-Heteroatom Substituted Allylic
Alcohols by Reaction of
(E)-a-Selanylvinylzirconiums or
(E)-a-Trimethylsilylvinylzirconiums with
Aldehydesy
Xian Huang* and Ai-Ming Sun
Department of Chemistry, Zhejiang University, Xi-xi Campus, Hangzhou 310028, P.R. China
Both (E)-a-selanylvinylzirconium and (E)-a-trimethylsilylvinylzirconium complexes undergo AgClO4-catalyzed reactions
with aldehydes to give a-seleno- or a-trimethylsilyl-substituted allylic alcohols, respectively.
Table 1 Preparation of a-selanylallylic alcohols 4a^d
Functionality-bearing allylic alcohols are often vital structural
units of biologically active compounds.1
number of
A
Entry
R
R1
R2
Product Yielda(%)
methods for the preparation of allylic alcohols have been pre-
viously reported, the most general method being Barbier
reactions.2 However, to date only the synthesis of
a-trimethylsilyl substituted allylic alcohols has been studied
to any extent,3 the synthesis of other a-heteroatom substituted
allylic alcohols has been little studied, and the synthesis of
a-selanyl substituted allylic alcohols has not been reported.
Vinylic selenides4 are very important intermediates in
organic synthesis and we thus attempt to develop a con-
venient method for synthesis of a-selanyl substituted allylic
alcohols.
(E)-a-Selanylvinylzirconium complexes can be synthesized
stereoselectively by hydrozirconation of internal acetylenic
selenides and we have studied the intermediates.5 Suzuki
and coworkers6 previously reported the addition of
vinylzirconocenes to aldehydes in the presence of a catalytic
amount of AgClO4 to give allylic alcohols as an extension
to our studies, we were interested in using this intermediate
to develop new synthetic routes toward a-selanyl substituted
allylic alcohols.
1
2
3
4
CH3OCH2
Bun
Et
Et
Et
Et
Prn
Prn
Ph
Ph
4a
4b
4c
4d
75
80
68
78
CH3OCH3
Bun
a Isolated yield.
Table 2 Preparation of a-trimethylsilylallylic alcohols 7a^d
Entry
R
R2
Product
Yielda(%)
1
2
3
4
MeOCH2
OCH2
MeBun
Bun
Prn
Ph
Prn
Ph
7a
7b
7c
7d
70
68
76
72
a Isolated yield.
O
R
H
SiMe3
R2
H
R
H
SiMe3
H
Cp2Zr(H)Cl
3
The results indicated that 2 can react with aldehydes 3
rapidly in CH2Cl2 at room temperature in the presence of
5 mmol% AgClO4 (Scheme 1), to a¡ord a-selanylallylic
alcohols in good yields (Table 1).
R
SiMe3
ZrCp2 AgClO4(cat.)
Cl
C
R2
5
OH
6
7
Scheme 2
In summary, we have developed a novel route to the syn-
thesis of a-heteroatom-substituted allylic alcohols, appli-
cations of these a-heteroatom substituted allylic alcohols
are currently being examined.
O
R
H
SeR1
R2
H
R
H
SeR1
H
Cp2Zr(H)Cl
3
R
SeR1
ZrCp2 AgClO4(cat.)
Cl
C
R2
1
OH
2
3
Experimental
1H NMR were recorded in CDCl3 on an AZ-300 spectrometer with
TMS as internal standard. Mass spectra were obtained using a Finigan
8230 mass spectrometer. The reactions were carried out in pre-dried
glassware (150 8C, 4 h) and cooled under a stream of dry nitrogen.
All solvents were dried, deoxygenated are redistilled before use.
General Procedure for the Synthesis of 4a^d.öA mixture of
Cp2ZrꢀH†Cl of (2 mmol) and acetylenic selenide 1 (2 mmol) in
CH2Cl2 (5 ml) was stirred at room temperature for 20 min. To the
resulting solution was added aldehyde 3 (1.8 mmol) in CH2Cl2 (5 ml)
followed by AgClO4 (90 mmol, 5 mmol%). The reaction mixture
turned dark gradually. After stirring for 15 min, the mixture was
poured into sat. NaHCO3 aqueous solutions. Extractive workup
(EtOAc) followed by puri¢cation with preparative TLC
(hexane^EtOAc, 411:1) gave a-seleno substituted allylic alcohols
4a-d:
Scheme 1
a-Trimethylsilylallylic alcohols have been synthesized
previously,3 but the reported method required low tempera-
ture and a number of steps, we report a simple method
for synthesizing a-trimethylsilylallylic alcohols. Intermediates
6 can be obtained by hydrozirconation of 1-trimethylsilylalk-1-
ynes 5, which can also react with aldehydes in the presence of
5 mmol% AgClO4 to provide a-trimethylsilylallylic alcohols
(Scheme 2). Results are listed in Table 2.
* To receive any correspondence.
Compound 4a. dH 6.25 (t, 1H), 4.12 (t, 1H), 3.85 (d, 2 H), 3.24 (s,
3 H), 2.58 (q, 2 H), 1.89 (s, 1H), 0.91^1.57 (m, 10 H). MS, m/z 252
y This is a Short Paper as de¢ned in the Instructions for Authors,
Section 5.0 [see J. Chem. Research (S), 1999, Issue 1]; there is
therefore no corresponding material in J. Chem. Research (M).
‡
(M ‡ 1) (Found : C, 47.49; H, 7.62; O, 12.49. C10H20SeO2 requires
C, 47.82; H, 8.03; O, 12.72%).

View Article Online
J. CHEM. RESEARCH (S), 1999 293
Compound 4b. dH 6.19 (t, 1H), 4.10 (t, 1H), 2.57 (q, 2 H), 1.85^2.29
Compound 7d. dH 7.10^7.50 (m, 5 H), 6.22 (t, 1H), 4.31 (s, 1H),
1.82^2.35 (m, 3 H), 0.92^1.60 (m, 7 H), 0.35 (s, 9 H). MS, m/z 262
‡
(m, 3 H), 0.90^1.58 (m, 17 H), MS, m/z 263 (M ‡ 1) (Found: C,
‡
54.39; H, 8.84; O, 5.79. C12H24SeO requires C, 54.74; H, 9.19; O,
6.07%).
(M ‡ 1) (Found: C, 73.45; H, 12.12; O, 6.43. C16H26SeO requires
C, 73.24; H, 9.99; O, 6.09%).
Compound 4c. dH 7.10^7.50 (m, 5 H), 6.23 (t, 1H), 4.35 (s, 1H), 3.85
(d, 2 H), 3.25 (s, 3 H), 2.59 (q, 2 H), 2.02 (s, 1H), 1.50 (t, 3 H).
Projects 29493800, 29772007 supported by National Natu-
ral Science Foundation of China. This work also supported
by the Laboratory of Organometallic Chemistry, Shanghai
Institute of Organic Chemistry, Academica Sinica.
‡
MS, m/z 285 (M ‡ 1) (Found: C, 54.54; H, 6.12; O, 11.00.
C13H18SeO2 requires C, 54.75; H, 6.36; O, 11.21%).
Compound 4d. dH 7.10^7.50 (m, 5 H), 6.20 (t, 1H), 4.33 (s, 1H), 2.56
(q, 2 H), 1.80^2.33 (m, 3 H), 0.92^1.60 (m, 10 H). MS, m/z 297
‡
(M ‡ 1) (Found: C, 60.49; H, 7.28; O, 5.17. C15H22SeO requires
C, 60.60; H, 7.46; O, 5.38%).
Received, 5th January 1999; Accepted, 21st January 1999
Paper E/9/00134
General Procedure for the Synthesis of 7a^d.öA mixture of
Cp2ZrꢀH†Cl (2 mmol) and 1-trimethylsilylalk-1-yne 5 (2 mmol) in
CH2Cl2 (5 ml) was stirred at room temperature for 1h. The following
steps were the same as for the synthesis of 4a^d.
Compound 7a. dH 6.25 (t, 1H), 4.15 (t, 1H), 3.95 (d, 2 H), 3.45 (s,
3 H), 2.15 (s, 1H), 1.15^1.61 (m, 7 H), 0.35 (s, 9 H). MS, m/z 217
‡
References
(M ‡ 1) (Found: C, 61.38; H, 11.47; O, 14.95. C11H24SeO2 requires
C, 61.07; H, 11.18; O, 14.77%).
1
J. Shimada and S. L. Schreiber, Chem. Eng. News, 1995, 73(37),
27.
Compound 7b. dH 7.05^7.46 (m, 5 H), 6.24 (t, 1H), 4.33 (s, 1H), 3.90
(d, 2 H), 3.43 (s, 37 H), 2.10 (s, 1H), 0.35 (s, 9 H). MS, m/z 250
2
3
C. J. li, Tetrahedron, 1996, 52, 5643.
‡
(M ‡ 1† (Found: C, 67.42; H, 8.94; O, 12.82. C14H22SeO2 requires
R. K. Boekman, Jr., D. M. Blum, B. Ganem and N. Halvery,
Org. Synth., 1978, 58, 152.
C, 67.16; H, 8.86; O, 12.76%).
Compound 7c. dH 6.18 (t, 1H), 4.10 (t, 1H), 1.86^2.27 (m, 3 H),
4
5
6
J. V. Comasseto, Organomet. Chem., 1983, 253, 131.
A. M. Sun and X. Huang, J. Chem. Res. (S), 1998, 616.
H. Maeta, T. Hashimoto, T. Hasegawa and K. Suzuki,
Tetrahedron Lett., 1992, 33, 5965.
‡
1.10^1.59 (m, 14 H), 0.34 (s, 9 H). MS, m/z 228 (M ‡ 1) (Found:
C, 68.53; H, 12.52; O, 7.30. C13H28SeO requires C, 68.35; H, 12.36;
O, 7.0 0 %).