A Pd-catalyzed organometallic-free homologation of arylboronic acids enabled by chemoselective transmetalation
Abstract
A Pd-catalyzed homologation of arylboronic acids is reported. Halomethylboronic acid pinacol esters (Bpin) undergo a remarkably facile, yet rare, oxidative addition enabled by an α-boryl effect. Simultaneous chemoselective transmetalation allows use of these metalloid reagents for formal C1 insertion to deliver benzyl Bpin products without the requirement for stoichiometric organometallic reagents. The utility of the process is demonstrated by stepwise C(sp3)–C(sp2) cross-coupling of the boronic ester products into diarylmethane pharmacophores and electrophile/nucleophile chemoselective cross-coupling. Control experiments that demonstrate the reactivity enhancement provided by the α-boryl effect are provided, along with a description of the limitations of the formal homologation process.
Citation
Bastick , K A C & Watson , A J B 2023 , ' A Pd-catalyzed organometallic-free homologation of arylboronic acids enabled by chemoselective transmetalation ' , ACS Catalysis , vol. 13 , no. 10 , pp. 7013–7018 . https://doi.org/10.1021/acscatal.3c00921
Publication
ACS Catalysis
Status
Peer reviewed
ISSN
2155-5435Type
Journal article
Description
Funding: K.A.C.B. thanks EPSRC and the University of St Andrews for a PhD studentship. A.J.B.W. thanks the Leverhulme Trust for a Research Fellowship (RF-2022-014) and the EPSRC Programme Grant “Boron: Beyond the Reagent” (EP/W007517) for support.Collections
Items in the St Andrews Research Repository are protected by copyright, with all rights reserved, unless otherwise indicated.