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Multistep electron transfer in palladium-catalyzed aerobic oxidations via a metal macrocycle-quinone system

Journal Article · · Journal of the American Chemical Society; (USA)
DOI:https://doi.org/10.1021/ja00169a025· OSTI ID:6653744

Selective palladium-catalyzed aerobic conditions of olefins and conjugated dienes with the aid of a metal macrocycle-quinone system have been developed. This involves a multistep electron transfer with three catalysts (Pd(OAc){sub 2}, hydroquinone, metal macrocycle). The triple catalytic system was applied to (i) 1,4-oxidation of conjugated dienes (1,4-diacetoxylation and 1,4-dialkoxylation), (ii) oxidation of terminal olefins to ketones, and (iii) allylic oxidation of cyclic olefins to 2-alken-1-yl acetates. The reactions occur under very mild conditions, (i) and (ii) at room temperature and (iii) at 60{degree}C, and are reminiscent of aerobic processes occurring in living organisms. Thus, there is an electron transfer from the substrate to Pd(II) giving Pd(0), followed by another electron transfer from Pd(0) to benzoquinone. The hydroquinone thus formed transfers electrons to the oxidized form of the metal macrocycle, which is reduced.

OSTI ID:
6653744
Journal Information:
Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:13; ISSN 0002-7863; ISSN JACSA
Country of Publication:
United States
Language:
English