Acyl rearrangements in radical reactions - The Journal of Organic

Model for the coenzyme B12-dependent methylmalonyl-CoA mutase reaction. Susan Wollowitz , Jack Halpern. Journal of the American Chemical Society 1984 ...
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J. Org. Chem., Vol. 37, No. 18, 1972

KARL,MAAS,AND REUSCH

Acyl Rearrangements in Radical Reactions CURTISL. KARL,E. JEROME MAAS,AND WILLIAMREUSCH* Department of Chemistry, Michigan State University, East Lansing, Michigan ,48883 Received March $1, 19% Solutions of the tert-butyl perlevulinate esters Ia,b,c undergo thermal decomposition (131") via radical intermediates. The latter two peresters give some unrearranged tert-butyl ethers, but the remaining products are exclusively derived from acyl rearranged radicals (e.g., methyl isobutyl ketone from I b and 4-phenyl-2-pentanone, 4-phenyl-3-penten-2-one, and 4-phenyl-4-penten-2-one from IC). No phenyl rearranged products (