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General Experimental
Procedure
To a solution of 1-octyne (165 mg, 1.5 mmol)
in dry THF (0.8 mL) cooled at -10 ˚C
was added i-PrMgCl˙LiCl (1 mL, 1.5
mmol, 1.5 M in THF) and stirred for 30 min at the same temperature.
To the so generated Grignard reagent, ZnBr2 (1.1 mL,
1.65 mmol, 1.5 M in THF) was added at 0 ˚C and stirred
for 30 min. To the organozinc reagent maintained at 0 ˚C
was added a solution of chloro sulfide (0.5 mmol) in benzene (5
mL), the reaction mixture stirred gradually allowing it to attain
r.t., and stirred further for a period of 7 h when TLC examination
indicated complete consumption of the chloro sulfide. The reaction
mixture was cooled to 0 ˚C and quenched by the
addition of an aq sat. NH4Cl solution. It was allowed
to warm to r.t. and diluted with
Et2O (5 mL),
the layers were separated and aqueous layer extracted with Et2O
(3 × 10 mL). The combined organic layers
were washed with H2O (5 mL), brine (5 mL), dried over
Na2SO4, and the solvent evaporated under reduced pressure
to afford a crude compound which was purified by column chromatography
using hexanes as the eluent to afford the pure product 9a (192 mg, 0.43 mmol) in 86% yield as
a liquid. TLC: R
f
= 0.34 (hexanes). IR (KBr):
3445, 3063, 2954, 2928, 1586, 1463, 1384, 1253, 1094, 827, 837,
777, 695 cm-¹. ¹H
NMR (200 MHz, CDCl3): δ = 7.60-7.30
(m, 10 H), 4.91 (d, J = 6.8
Hz, 1 H), 4.16 (td, J = 2.3,
6.8 Hz, 1 H), 2.16 (dt, J = 2.3,
6.8 Hz, 2 H), 1.50-1.15 (m, 8 H), 1.00-0.90 (m,
12 H), 0.20 (s, 3 H), 0.0 (s, 3 H). ¹³C
NMR (75 MHz, CDCl3): δ = 142.00, 135.62,
132.11, 128.58, 127.82, 127.69, 127.36, 126.89, 87.32, 77.45, 48.91,
31.45, 28.51, 28.47, 25.89, 22.62, 18.35, 14.20, -4.55, -4.83.
ESI-MS: m/z 469 [M + NH4]+.
ESI-HRMS: m/z calcd for C28H40ONaSiS: 475.2467;
found: 475.2466.
18 Substrate 13 was
prepared by deprotection of acetonide moiety in 10 followed
by protection of the resulting diol, see Supporting Information.
19 The signals for the olefinic, methine
protons of the acetonide and CH
2OBn
appear downfield in ester 18 compared to
the corresponding protons of ester 19,
see Supporting Information.
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