Aerobic palladium-catalyzed dioxygenation of alkenes enabled by catalytic nitrite.
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.
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125 (USA).
Zachary K
ZK
Wickens
Pablo E
PE
Guzmán
Robert H
RH
Grubbs
D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D009573:Nitrites / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D010165:Palladium / Q000737:chemistry*
D000475:Alkenes; D009573:Nitrites; D010165:Palladium; D010100:Oxygen
alkenes; high-valent palladium; nitrite; oxidation; oxygen