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1,2‐Asymmetric Induction in the Ketene Claisen Rearrangement of Allyl Sulfides
Author(s) -
Nubbemeyer Udo,
Öhrlein Reinhold,
Gonda Jozef,
Ernst Beat,
Belluš Daniel
Publication year - 1991
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.199114651
Subject(s) - ketene , optically active , claisen rearrangement , chemistry , asymmetric induction , carroll rearrangement , medicinal chemistry , stereochemistry , combinatorial chemistry , enantioselective synthesis , organic chemistry , catalysis
Optically active α‐siloxycarbonates are converted to optically active allylsulfides 1 . These intermediates are allowed to react with dichloroketene (generated in situ) leading to optically active α,α‐dichloro‐β‐vinyl‐γ‐siloxy‐substituted thioesters 2 . The assumed transition state is represented by 3 . This ketene‐Claissen rearrangement shows complete 1,2‐asymmetric induction in all of the cases examined. Reductive dechlorination of the γ‐siloxy‐substituted thioesters provides optically active 3,4‐ cis ‐distubstituted γ‐lactones. R = Me, i Pr, C 2 H 4 OTBDMS; TBDMS = tert ‐butyldimethylsilyl.