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CC BY 4.0 · Synlett 2023; 34(18): 2097-2102
DOI: 10.1055/a-2117-9878
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Modern Boron Chemistry: 60 Years of the Matteson Reaction

Pd-Catalyzed Homologation of Arylboronic Acids as a Platform for the Diversity-Oriented Synthesis of Benzylic C–X Bonds

Kane A. C. Bastick
,
Allan J. B. Watson  ∗
K.A.C.B thanks the Engineering and Physical Sciences Research Council (EPSRC, Grant Number EP/W007517) and the University of St Andrews for a PhD studentship. A.J.B.W. thanks the Leverhulme Trust for a Research Fellowship and the EPSRC Programme Grant ‘Boron: Beyond the Reagent’ for support.
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Dedicated to Prof. Donald S. Matteson on the 60th anniversary of the reaction that bears his name.

Abstract

We report a synthetic platform for the formation of benzylic C–X bonds. Benzylboronic acid pinacol (Bpin) esters are useful synthetic intermediates but are commercially uncommon, leading to preparations that typically rely upon stoichiometric metalation. Pd-catalyzed formal homologation of arylboronic acids provides access to these compounds that, in turn, allow the formation of C–C, C–O, and C–N bonds from Pd- and Cu-mediated cross-coupling or oxidative processes. This affords a wide variety of benzylic alcohols, diarylmethanes, benzyl amines, and benzyl ethers. Limitations are disclosed, and the utility is further demonstrated by the generation of analogues of meclizine.

Key words

boron - catalysis - chemoselectivity - homologation - diversity-oriented synthesis

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2117-9878.
  • Supporting Information


Publication History

Received: 02 June 2023

Accepted after revision: 22 June 2023

Accepted Manuscript online:
26 June 2023

Article published online:
15 August 2023

© 2023. This is an open access article published by Thieme under the terms of the Creative Commons Attribution License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by/4.0/)

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