Haloboration of o‐Alkynyl Phenols Generates Halogenated Bicyclic‐Boronates

Kang Yuan, Michael Ingleson

Research output: Contribution to journalArticlepeer-review

Abstract

Benzoxaborinines are intermediates en-route to bicyclic boronates that are important active pharmaceutical ingredients (APIs). Herein, the haloboration of o-alkynyl-phenols using BX3 (X = Cl or Br) is disclosed as a route to form C4-X-benzoxaborinines with good functional group tolerance. Computational studies indicated that there are two similar in barrier mechanisms: (i) double alkyne haloboration followed by retro-haloboration; (ii) concerted trans-haloboration involving an exogenous chloride source. The C4-halide in these benzoxaborinines is useful, with a one-pot haloboration-Negishi cross coupling protocol effective to form benzoxaborinines with an alkyl or an aryl at C4. Therefore this method is a useful addition to the toolbox for synthesizing bicyclic-boronates that are attracting increasing attention as APIs.
Original languageEnglish
JournalAngewandte Chemie International Edition
Early online date1 Mar 2023
DOIs
Publication statusE-pub ahead of print - 1 Mar 2023

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