Rh-Catalyzed Desymmetrization of α-Quaternary Centers by Isomerization-Hydroacylation.
We describe a Rh-catalyzed desymmetrization of all-carbon quaternary centers from α,α-bis(allyl)aldehydes by a cascade featuring isomerization and hydroacylation. This desymmetrization competes with two other novel olefin functionalizations that are triggered by C-H bond activation, including carboacylation and bisacylation. A BIPHEP ligand promotes enantioselective formation of α-vinylcyclopentanones. Mechanistic studies support irreversible and enantioselective olefin-isomerization followed by olefin-hydroacylation.
Department of Chemistry, University of California-Irvine, 4403 Natural Sciences 1, Irvine, California 92697, USA.
Jung-Woo
JW
Park
Department of Chemistry, University of California-Irvine, 4403 Natural Sciences 1, Irvine, California 92697, USA.
Kevin G M
KG
Kou
Department of Chemistry, University of California-Irvine, 4403 Natural Sciences 1, Irvine, California 92697, USA.
Daniel K
DK
Kim
Department of Chemistry, University of California-Irvine, 4403 Natural Sciences 1, Irvine, California 92697, USA.
Vy M
VM
Dong