Stereochemistry of the Kulinkovich cyclopropanation of nitriles.
The stereochemistry of the Kulinkovich cyclopropanation of nitriles with alkenes has been examined by employing (E)-disubstituted alkenes and deuterium-labeled homoallylic alcohols as a stereochemical probe. An intramolecular cyclopropanation proceeds with preservation of the olefin configuration. On the other hand, intermolecular counterparts occur with both preservation and reversal of the olefin configuration, which corresponds to retention and inversion of configuration at the Ti-C bond, respectively, in the cyclopropane-forming step. These uncommon stereochemical outcomes contrast with that of the Kulinkovich cyclopropanation of tertiary amides.
Astashko
Dmitry
D
Department of Chemistry, Wayne State University, 5101 Cass Avenue, Detroit, Michigan 48202, USA.
Lee
Hyung Goo
HG
Bobrov
Denis N
DN
Cha
Jin K
JK
D000475:Alkenes / Q000737:chemistry; D003500:Cyclization; D003521:Cyclopropanes / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry*; D013237:Stereoisomerism
D000475:Alkenes; D003521:Cyclopropanes; D009570:Nitriles