Year: 2023
Type: article
Abstract: We describe a copper catalyst that promotes the addition of phosphines to cyclopropenes at ambient temperature. A range of cyclopropylphosphines bearing different steric and electronic properties can now be accessed in high yields and enantioselectivities. Enrichment of phosphorus stereocenters is also demonstrated via a Dynamic Kinetic Asymmetric Transformation (DyKAT) process. A combined experimental and theoretical mechanistic study supports an elementary step featuring insertion of a Cu I ‐phosphido into a carbon‐carbon double bond. Density functional theory calculations reveal migratory insertion as the rate‐ and stereo‐determining step, followed by a syn‐ protodemetalation.
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
Awards: CAS: Sustainable Technologies for Building Molecules: Cobalt, Nickel, and Copper Catalysis, G1742171491, G2206590661, G2295412010, G309578167, G3147773666, G3226045097, G3405329159, XSEDE 2.0: Integrating, Enabling and Enhancing National Cyberinfrastructure with Expanding Community Involvement, Sustainable Technologies for Building Molecules: Ethers, Phosphines, and Amino Acids, G7007390191, G793687321, Innovative Tools for Chemical Synthesis: Metal-Hydride Catalysis, Medicinal Motifs, and Molecular Probes, Mechanistic Investigation into Modern Catalytic Reactions
OpenAlex ID: W4381123826