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The Stereochemistry of Carbenoid Cyclopropanation Reactions
Author(s) -
Stiasny Hans Christian,
Hoffmann Reinhard W.
Publication year - 1995
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.19950010909
Subject(s) - cyclopropanation , carbenoid , intramolecular force , diastereomer , chemistry , substituent , stereochemistry , bicyclic molecule , hexane , medicinal chemistry , organic chemistry , rhodium , catalysis
The stereochemical course of the intramolecular carbenoid cyclopropanation reaction has been studied for the epimeric carbenoids 12a and 12b . In these reactions the tert ‐butyldimethylsilyloxy substituent serves as an internal stereochemical reference point. It was found that 12b cyclizes rapidly at −110°C in a complexation‐assisted concerted process to give the bicyclo[3.1.0]hexane 16 . The diastereomer 12a cyclizes more slowly at −100°C to give both 16 and 17 ; the former is probably formed by a complexation‐assisted carbolithiation pathway.