TY - JOUR
T1 - Aerobic Palladium-Catalyzed Dioxygenation of Alkenes Enabled by Catalytic Nitrite
AU - Wickens, Zachary K.
AU - Guzman, Pablo E.
AU - Grubbs, Robert H.
N1 - KAUST Repository Item: Exported on 2021-10-08
Acknowledgements: We gratefully acknowledge financial support from the King Abdullah University of Science and Technology Centre in Development, King Fahd University of Petroleum and Minerals, the NSF (CHE 1212767), NIH (R01GM031332), and the Gordon and Betty Moore Foundation. P.E.G. is grateful to the NIH for a postdoctoral fellowship.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.
PY - 2015
Y1 - 2015
N2 - Catalytic nitrite was found to enable carbon-oxygen bond-forming reductive elimination from unstable alkyl palladium intermediates, providing dioxygenated products from alkenes. Avariety 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 18O-labeling experiments, which demonstrated that both oxygen atoms in the difunctionalized products were derived from one molecule of acetic acid.
AB - Catalytic nitrite was found to enable carbon-oxygen bond-forming reductive elimination from unstable alkyl palladium intermediates, providing dioxygenated products from alkenes. Avariety 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 18O-labeling experiments, which demonstrated that both oxygen atoms in the difunctionalized products were derived from one molecule of acetic acid.
UR - http://hdl.handle.net/10754/672264
UR - http://doi.wiley.com/10.1002/anie.201408650
UR - http://www.scopus.com/inward/record.url?scp=84920120754&partnerID=8YFLogxK
U2 - 10.1002/anie.201408650
DO - 10.1002/anie.201408650
M3 - Article
SN - 1521-3773
VL - 54
SP - 236
EP - 240
JO - ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
JF - ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
IS - 1
ER -