The Journal of Organic Chemistry

Mechanism of the photochemical Wolff rearrangement. The role of conformation in the photolysis of. alpha.-diazo carbonyl compounds

H Tomioka, H Okuno, Y Izawa

Index: Tomioka, Hideo; Okuno, Hiroshi; Izawa, Yasuji Journal of Organic Chemistry, 1980 , vol. 45, # 26 p. 5278 - 5283

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Citation Number: 59

Abstract

Investigation of photochemical processes of several a-diazo carbonyl compounds reveals that the Wolff rearrangement, to form ketene takes place directly from the singlet excited state of the s-2 conformer whereas the excited state of the sE conformer dissociates nitrogen to generate singlet carbonyl carbene, which either undergoes characteristic carbenic reactions, eg, insertion and 1, 2-hydrogen shift, or gives rise to ketene. The migratory ...