Affiliation:
1. Department of Biochemistry The University of Texas Southwestern Medical Center 5323 Harry Hines Boulevard Dallas TX 75390-9038 USA
2. Department of Chemistry Korea Advanced Institute of Science and Technology (KAIST) Daejeon 34141 Republic of Korea
3. Center for Catalytic Hydrocarbon Functionalizations Institute for Basic Science (IBS) Daejeon 34141 Republic of Korea
Abstract
AbstractWe report a copper‐catalyzed, regioselective, and stereospecific alkylation of unbiased internal allylic carbonates with functionalized alkyl and aryl Grignard reagents. The reactions exhibit high stereospecificity and regioselectivity for either SN2 or SN2′ products under two sets of copper‐catalyzed conditions, which enables the preparation of a broad range of products with E‐alkene selectivity. Density functional theory calculations reveal the origins of the regioselectivity based on the different behaviors of homo‐ and heterocuprates.
Funder
W. W. Caruth, Jr. Foundation
Welch Foundation
Foundation for the National Institutes of Health
American Chemical Society Petroleum Research Fund
Teva Pharmaceutical Industries
Alfred P. Sloan Foundation
Institute for Basic Science