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Stereochemistry of Thermally‐Induced Homolytic Fission of C‐C Bonds in Small Rings
Author(s) -
Gajewski Joseph J.
Publication year - 1981
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.198100035
Subject(s) - conrotatory and disrotatory , chemistry , homolysis , cyclopropane , ring (chemistry) , stereochemistry , single bond , rotation (mathematics) , computational chemistry , radical , organic chemistry , alkyl , geometry , mathematics
This is a review of the pertinent literature on the subject of the stereochemistry of homolytic nonconcerted ring opening of small carbocycles. The data suggests that cyclopropane opens either without bond rotation or with a single rotation or with disrotatory double rotation; conrotatory double rotation has not yet been observed. Cyclobutane and cyclopentane undergo conrotatory ring opening that is coupled with another rotation to cause shearing of the bond to give a gauche 1,4‐ or 1, 5‐biradical. These biradicals apparently undergo bond formation with rearrangement via a least motion stereochemical pathway competitive with rotation around bonds to randomize the stereochemistry of the initially generated biradical.