Copper-Phosphido Catalysis: Enantioselective Addition of Phosphines to Cyclopropenes

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. A combined experimental and theoretical mechanistic study supports insertion of a Cu(I)-phosphido intermediate into the strained olefin. Density functional theory calculations reveal migratory insertion as the stereodetermining step of the pathway, with final product formation occurring via a syn-protodemetalation. Enrichment of phosphorus stereocenters is demonstrated via a DyKAT process.

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Expansion of the introduction and minor edits throughout

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Copper-Phosphido Catalysis: Enantioselective Addition of Phosphines to Cyclopropenes
Reaction Protocols, Computational Protocols