Synthesis of Vinyl-, Allyl-, and 2-Boryl Allylboronates via a Highly Selective Copper-Catalyzed Borylation of Propargylic Alcohols.

Org Lett

Institut für Anorganische Chemie and Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, 97074 Würzburg, Germany.

Published: December 2017

An efficient methodology for the synthesis of vinyl-, allyl-, and (E)-2-boryl allylboronates from propargylic alcohols via Cu-catalyzed borylation under mild conditions is reported. In the presence of commercially available Cu(OAc) or Cu(acac) and Xantphos, the reaction affords the desired products in up to 92% yield with a broad substrate scope (43 examples). Isolation of an allenyl boronate as the reaction intermediate suggests that an insertion-elimination-type reaction, followed by borylcupration, is involved in the borylation of propargylic alcohols.

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http://dx.doi.org/10.1021/acs.orglett.7b03294DOI Listing

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