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First Examples of a Claisen Rearrangement Stereocontrolled by a Sulfinyl Group: Synthesis of Novel α‐Sulfinyl Dithioesters
Author(s) -
Alayrac Carole,
Fromont Christophe,
Metzner Patrick,
Anh Nguyen Trong
Publication year - 1997
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.199703711
Subject(s) - ketene , diastereomer , chemistry , sulfenic acid , claisen rearrangement , carroll rearrangement , sulfoxide , sigmatropic reaction , allene , stereochemistry , group (periodic table) , medicinal chemistry , organic chemistry , catalysis , cysteine , enzyme
Diastereomeric excesses up to 98% are a characteristic of the Claisen rearrangement of ketene dithioacetals 1 , which contain a chiral sulfinyl group, to afford γ‐unsaturated α‐sulfinyl dithioesters 2 . This reaction is the first example of a [3,3] rearrangement whose stereochemical course is controlled by a sulfinyl group. Owing to the mild thermal conditions (room temperature) undesired elimination of sulfenic acid was not observed.