106058-83-7Relevant academic research and scientific papers
An Acylative C-C Single-Bond Cleavage and a Self-Cyclization of Ethyl 2-(Trimethylsilylmethyl)penta-2,4-dienoate or Its Free Acid under Ritter Condition
Kuroda, Chiaki,Mitsumata, Naoko,Tang, Chen Ying
, p. 1409 - 1416 (1996)
An acylative C(3)-C(4)-bond cleavage of ethyl 4,5-disubstituted 2-(trimethylsilylmethyl)penta-2,4-dienoate occurred to give an ethyl 2-(2-oxoalkyl)acrylate by treatment with trifluoromethanesulfonic acid in nitriles. A self-cyclization also occurred to give a 5,5-disubstituted 3-methylenetetrahydrofuran-2-one when the reactions were carried out in bulky nitriles. Only self-cyclization proceeded when the corresponding 4,5-disubstituted 2-(trimethylsilylmethyl)penta-2,4-dienoic acid was treated in acetonitrile. The reaction mechanism is described.
REACTIONS RELATED TO COENZYME B12 DEPENDENT REARRANGEMENTS: METAL MEDIATED FREE RADICAL ACYL MIGRATIONS IN METHYL AND CYCLOPROPYL SUBSTITUTED MODELS
Best, Wayne M.,Widdowson, David A.
, p. 5943 - 5954 (2007/10/02)
Free radicals generated from the methylmalonylcoenzyme A mutase model substrates (3) and (4) by chromium(II) reduction, or by pyrolysis of the analogous cobaloximes, underwent -migration only in the acyl series (R=Ph, Me) and not the critical ester series (R=OEt, SBu).The mechanism of the migration was implied by incorporation into (4) of the cyclopropyl ring, the opening of which demonstrated the free radical nature of rearranged intermediate.
