A Highly Regioselective Reaction of Allylic Acetates with Silylated Carbon Nucleophiles Directed by a Sulfenyl Group. Scope, Limitation, and Mechanistic Aspects

α-(Sulfenylmethyl)allyl acetates reacted with silylated carbon nucleophiles in the presence of a catalytic amount of TMSOTf to give products substituted at the α-position of the sulfenylmethyl group in moderate to good yields with high regioselectivity. The theoretical calculation on an intermediate...

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Bibliographic Details
Published inBulletin of the Chemical Society of Japan Vol. 66; no. 3; pp. 848 - 856
Main Authors Kudo, Kazuaki, Hashimoto, Yukihiko, Houchigai, Hitoshi, Hasegawa, Masaki, Saigo, Kazuhiko
Format Journal Article
LanguageEnglish
Published TOKYO The Chemical Society of Japan 01.03.1993
Chemical Soc Japan
Chemical Society of Japan
Subjects
Aliphatic compounds
Chemistry
Chemistry, Multidisciplinary
Exact sciences and technology
Organic chemistry
Physical Sciences
Preparations and properties
Science & Technology
ORGANIC-SYNTHESIS
OLEFINS
CARBOSULFENYLATION
ALKYLATION
Nucleophilic reaction
Regioselectivity
Aliphatic compound
Reaction mechanism
Enol ether
Acylate
Ketone
Allylic compound
Organic sulfide
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Summary:α-(Sulfenylmethyl)allyl acetates reacted with silylated carbon nucleophiles in the presence of a catalytic amount of TMSOTf to give products substituted at the α-position of the sulfenylmethyl group in moderate to good yields with high regioselectivity. The theoretical calculation on an intermediate cationic species indicated that an episulfonium ion was a stable form; the observed regioselectivity was rationalized qualitatively on the basis of the coefficients of LUMO of the cation. Some transformations of the products were also demonstrated.
ISSN:0009-2673
1348-0634
DOI:10.1246/bcsj.66.848