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Aerobic Palladium‐Catalyzed Dioxygenation of Alkenes Enabled by Catalytic Nitrite
Author(s) -
Wickens Zachary K.,
Guzmán Pablo E.,
Grubbs Robert H.
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201408650
Subject(s) - chemistry , catalysis , palladium , nitrite , alkyl , reductive elimination , catalytic cycle , oxygen , acetic acid , molecule , photochemistry , combinatorial chemistry , organic chemistry , functional group , nitrate , polymer
Abstract Catalytic nitrite was found to enable carbon–oxygen bond‐forming reductive elimination from unstable alkyl palladium intermediates, providing dioxygenated products from alkenes. A variety of functional groups were tolerated, and high yields (up to 94 %) were observed with many substrates, also for a multigram‐scale reaction. Nitrogen dioxide, which could form from nitrite under the reaction conditions, was demonstrated to be a potential intermediate in the catalytic cycle. Furthermore, the reductive elimination event was probed with 18 O‐labeling experiments, which demonstrated that both oxygen atoms in the difunctionalized products were derived from one molecule of acetic acid.