Carbenylative Amination and Alkylation of Vinyl Iodides via Palladium Alkylidene Intermediates.
Most palladium-catalyzed reactions involving insertion of alkylidenes with α-hydrogens undergo β-hydride elimination from alkylpalladium(II) intermediates to form alkenes. Vinyl iodides were shown to generate η(3)-allylpalladium intermediates that resist β-hydride elimination, preserving the sp(3) center adjacent to the carbene moiety. Acyclic stereocontrol (syn/anti) for carbenylative amination and alkylation reactions was low, suggesting a lack of control in the migratory insertion step. Highly hindered carbene precursors inexplicably led to formation of Z-alkenes with high levels of stereocontrol.
Department of Chemistry, University of California , 1102 Natural Sciences 2, Irvine, California 92697-2025, United States.
Ilandari Dewage Udara Anulal
ID
Premachandra
Department of Chemistry, University of California , 1102 Natural Sciences 2, Irvine, California 92697-2025, United States.
Thi A
TA
Nguyen
Department of Chemistry, University of California , 1102 Natural Sciences 2, Irvine, California 92697-2025, United States.
Chengtian
C
Shen
Department of Chemistry, University of California , 1102 Natural Sciences 2, Irvine, California 92697-2025, United States.
Eugene S
ES
Gutman
Department of Chemistry, University of California , 1102 Natural Sciences 2, Irvine, California 92697-2025, United States.
David L
DL
Van Vranken