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Experimental and theoretical studies on the mechanism of 1,2‐migration of vinyl and formyl substituents in free radicals
Author(s) -
Giese Bernd,
Heinrich Nikolaus,
Horler Hans,
Koch Wolfram,
Schwarz Helmut
Publication year - 1986
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19861191203
Subject(s) - chemistry , cyclopropane , radical , ab initio , medicinal chemistry , ab initio quantum chemistry methods , reaction mechanism , stereochemistry , computational chemistry , molecule , organic chemistry , ring (chemistry) , catalysis
Vinyl and formyl groups undergo rearrangements of the type XCH CMe 2 ĊH 2 → ĊMe 2 CH 2 CHX (XCH 2 or O) with comparable rates (10 6 10 7 l/mol · s, 20°C). This result is in line with high‐level ab initio calculations performed on the basic systems, i.e. XCH CH 2 ĊH 2 , which give barriers of activation of 14.9 (CH 2 CH CH 2 ĊH 2 ) and 19.2 kcal/mol (OCH CH 2 ĊH 2 ), respectively. The calculations suggest that the rearrangements proceed via cyclopropane‐like intermediates.