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. 2020 Jul 1;142(26):11382-11387.
doi: 10.1021/jacs.0c05343. Epub 2020 Jun 23.

Bismuth-Catalyzed Oxidative Coupling of Arylboronic Acids with Triflate and Nonaflate Salts

Oriol Planas  1 , Vytautas Peciukenas  1 , Josep Cornella  1
Affiliations

Bismuth-Catalyzed Oxidative Coupling of Arylboronic Acids with Triflate and Nonaflate Salts

Oriol Planas et al. J Am Chem Soc. .

Abstract

Herein we present a Bi-catalyzed cross-coupling of arylboronic acids with perfluoroalkyl sulfonate salts based on a Bi(III)/Bi(V) redox cycle. An electron-deficient sulfone ligand proved to be key for the successful implementation of this protocol, which allows the unusual construction of C(sp2)-O bonds using commercially available NaOTf and KONf as coupling partners. Preliminary mechanistic studies as well as theoretical investigations reveal the intermediacy of a highly electrophilic Bi(V) species, which rapidly eliminates phenyl triflate.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
(A) OTf anions as ligands in transition metal chemistry. (B) Catalytic Ar–OTf formation through a Bi(III)/Bi(V) redox system.
Figure 2
Figure 2
(A) Study of the transmetalation step: influence of the molecular sieves and the base. (B) Stoichiometric sequence of oxidative addition–reductive elimination. (C) Theoretical analysis of the C–O bond forming step. aYields determined by 1H NMR using 1,3,5-trimethoxybenzene as internal standard. bYields determined by 19F NMR using 1-fluoro-4-nitrobenzen as internal standard.
Figure 3
Figure 3
Postulated mechanism for the Bi-catalyzed oxidative coupling of arylboronic acids and triflate salts.
See this image and copyright information in PMC

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