Interrogating Pd(II) anion metathesis using a bifunctional chemical probe : a transmetalation switch

Molloy, John J. and Seath, Ciaran P. and West, Matthew J. and McLaughlin, Calum and Fazakerley, Neal J. and Kennedy, Alan R. and Nelson, David J. and Watson, Allan J. B. (2018) Interrogating Pd(II) anion metathesis using a bifunctional chemical probe : a transmetalation switch. Journal of the American Chemical Society, 140 (1). pp. 126-130. ISSN 1520-5126 (https://doi.org/10.1021/jacs.7b11180)

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Abstract

Ligand metathesis of Pd(II) complexes is mechanistically essential for cross-coupling. We present a study of halide→OH anion metathesis of (Ar)Pd(II) complexes using vinylBPin as a bifunctional chemical probe with Pd(II)-dependent cross-coupling pathways. We identify the variables that profoundly impact this event and allow control to be leveraged. This then allows control of cross-coupling pathways via promotion or inhibition of organoboron transmetalation, leading to either Suzuki-Miyaura or Mizoroki-Heck products. We show how this transmetalation switch can be used to synthetic gain in a cascade cross-coupling/Diels-Alder reaction, delivering borylated or non-borylated carbocycles, including steroid-like scaffolds.

ORCID iDs

Molloy, John J. ORCID logoORCID: https://orcid.org/0000-0002-0538-7852, Seath, Ciaran P. ORCID logoORCID: https://orcid.org/0000-0002-6774-128X, West, Matthew J., McLaughlin, Calum, Fazakerley, Neal J., Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Nelson, David J. ORCID logoORCID: https://orcid.org/0000-0002-9461-5182 and Watson, Allan J. B.;
  • Item type:Article
    ID code:62678
    Dates:
    Date
    Event
    10 January 2018
    Published
    22 December 2017
    Published Online
    19 December 2017
    Accepted
    Notes:This document is the unedited Author's version of a Submitted Work that was subsequently accepted for publication in Journal of the American Chemical Society, copyright © American Chemical Society after peer review. To access the final edited and published work see https://doi.org/10.1021/jacs.7b11180
    Subjects:Science > Chemistry > Physical and theoretical chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:21 Dec 2017 09:56
    Last modified:19 Nov 2024 01:10
    URI:https://strathprints.strath.ac.uk/id/eprint/62678
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