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Synthesis and Reactions of a Stable Precursor to Dienes Containing Both Silicon and Sulfur Substituents
Author(s) -
Chou ShangShing P.,
Tsai ChungYing,
Sun ChungMing
Publication year - 1989
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.198900034
Subject(s) - chemistry , trimethylsilyl , carbanion , butyllithium , alkylation , medicinal chemistry , sulfonyl , organic chemistry , sulfur , catalysis , alkyl
3‐(Phenylthio)‐4‐(trimethylsilyl)‐3‐sulfolene (2) was readily prepared by chlorosulphenylation‐dehydrochlorination of 3‐(trimethylsilyl)‐3‐sulfolene (4b) . Treatment of 2 with n‐butyllithium at −105 °C followed by an alkylating agent gave only C5 alkylation products 6 demonstrating the stronger carbanion stabilizing ability of phenylthio group than that of trimethylsilyl group. 2‐(Phenylthio)‐3(trimethylsilyl)‐1,3‐butadiene (3a) was readily prepared by thermal extrusion of sulfur dioxide from 2 . Selective oxidation of 3a with MCPBA gave the sulfinyl (3b) and sulfonyl (3c) derivatives. The Diels‐Alder reactions of 3a‐c were studied, and the regiocontrolling power of the substituents follows the order PhS >PhSO ∼ PhSO 2 >Me 3 Si.