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The Belluš–Claisen Rearrangement
Author(s) -
Gonda Jozef
Publication year - 2004
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.200301718
Subject(s) - claisen rearrangement , sigmatropic reaction , allylic rearrangement , thioether , chemistry , ketene , carroll rearrangement , rearrangement reaction , cope rearrangement , ring (chemistry) , ether , amide , stereochemistry , medicinal chemistry , organic chemistry , catalysis
Abstract Among the reactions available to synthetic chemists for the construction of new CC bonds, the Claisen rearrangement is one of the most powerful, elegant, and well‐characterized methods. A genuinely new variant, the Belluš–Claisen rearrangement came to light a quarter of a century ago: The reaction of an allylic ether, thioether, or amine with a ketene leads through a [3,3] sigmatropic bond reorganization of a zwitterionic intermediate to an E unsaturated ester, thioester, or amide. When applied to cyclic allylic substrates, a ring‐enlargement by four carbon atoms in one step provides medium‐ring unsaturated E ‐configured lactones, thiolactones, and lactams. The scope of the Belluš–Claisen rearrangement and the optimum reaction conditions will be discussed in this Minireview.