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Copper-catalyzed stereo- and regioselective hydrophosphorylation of terminal alkynes: scope and mechanistic study† † Electronic supplementary information (ESI) available. See https://doi.org/10.1039/d2ra02908a

ABSTRACT: Herein, a protocol for copper-catalyzed highly stereo- and regioselective hydrophosphorylation of terminal alkynes to E-alkenylphosphorus compounds was well developed. It represents a general and practical hydrophosphorylation method, of which diarylphosphine oxide, dialkylphosphine oxide and dialkyl phosphite all had effective P(O)H parts to react with different types of terminal alkynes. Contrary to previous air-sensitive reports, all the reactions proceeded well under air. This methodology is quite attractive owing to the high stereo- and regioselectivity, good functional group tolerance, scalability and facile late-stage derivatization of some natural product derivatives and commercially available herbicides. What's more, investigations on the reaction mechanism with deuterium-labeling experiments and DFT studies firstly disclosed the deprotonation–protonation equilibrium of terminal alkynes and P(O)H part during the catalytic hydrophosphorylation process. A highly selective hydrophosphorylation of terminal alkynes was developed for the preparation of E-alkenylphosphorus compounds. Mechanistic investigations disclosed the deprotonation–protonation equilibrium of terminal alkynes and P(O)H compounds during this process.

SUBMITTER: Li J

PROVIDER: S-EPMC9241361 | biostudies-literature | 2022 Jun

REPOSITORIES: biostudies-literature

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