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Selectivity of Intramolecular Radical Addition Reactions Cyclization of ω‐Alkenyl Radicals
Author(s) -
Bischof Peter
Publication year - 1980
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19800630613
Subject(s) - mindo , chemistry , radical , intramolecular force , methylene , selectivity , chain reaction , photochemistry , computational chemistry , medicinal chemistry , stereochemistry , organic chemistry , molecule , catalysis
Small ω‐alkenyl radicals are known to cyclize exclusively via the unexpected Anti‐Markownikow pathway which leads to cycloalkyl‐methyl radicals as the observed reaction products. The strong kinetic preference diminishes, as the linking methylene chain becomes larger. Semiempirical calculations using MINDO/3‐UHF allow to classify the observed reaction pathways as individual probes between allowed (n = 1, route A ) and electronically favourable (n = ∞, route M ) routes of reactions.