Affiliation:
1. Department of Chemistry The Scripps Research Institute 10550 North Torrey Pines Road CA 92037 La Jolla USA
2. Department of Chemistry University of Pittsburgh 219 Parkman Avenue PA 15260 Pittsburgh USA
3. Automated Synthesis Facility The Scripps Research Institute 10550 North Torrey Pines Road CA 92037 La Jolla USA
Abstract
AbstractThe catalytic enantioselective synthesis of α‐chiral alkenes and alkynes represents a powerful strategy for rapid generation of molecular complexity. Herein, we report a transient directing group (TDG) strategy to facilitate site‐selective palladium‐catalyzed reductive Heck‐type hydroalkenylation and hydroalkynylation of alkenylaldehyes using alkenyl and alkynyl bromides, respectively, allowing for construction of a stereocenter at the δ‐position with respect to the aldehyde. Computational studies reveal the dual beneficial roles of rigid TDGs, such as L‐tert‐leucine, in promoting TDG binding and inducing high levels of enantioselectivity in alkene insertion with a variety of migrating groups.
Funder
National Institute of General Medical Sciences
Research Corporation for Science Advancement
National Science Foundation
National Institutes of Health