Regio- and Stereoselective Addition of Secondary Phosphine Oxides to Allenoates Catalyzed by Main-Group Lewis Pairs

Soojin Kwak, Jeongin Choi, Jimin Han, Sarah Yunmi Lee

Research output: Contribution to journalArticlepeer-review

7 Citations (Scopus)

Abstract

We report herein a Lewis pair-catalyzed process for the regio- and stereoselective addition of secondary phosphine oxides (SPOs) to allenoates. A Lewis pair composed of B(C6F5)3 and P(4-OMeC6H4)3 dissociates into a free acid and base under reaction conditions, thereby creating key reaction intermediates that enable the atom-economical generation of an array of alkenylphosphorus building blocks. Mechanistic studies indicate that this process proceeds through a catalytic cycle wherein the deprotonation of a P-H bond of a SPO (coordinated to a boron catalyst) by the phosphonium zwitterion (resulting from the nucleophilic addition of a phosphine catalyst to allenoates) is the rate-determining step. Subsequent addition of the phosphinite anion to allenoate substrates furnishes β-addition products, while the reaction between the pair of the phosphinite anion and alkenylphosphonium cation affords γ-addition products.

Original languageEnglish
Pages (from-to)212-218
Number of pages7
JournalACS Catalysis
Volume12
Issue number1
DOIs
Publication statusPublished - 2022 Jan 7

Bibliographical note

Publisher Copyright:
© 2021 American Chemical Society.

All Science Journal Classification (ASJC) codes

  • Catalysis
  • General Chemistry

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