Experimental and computational insights into the mechanism of the copper(I)-catalysed sulfonylative Suzuki-Miyaura reaction

Helen Sneddon; Callum Hall; Peter Pogany; David Lindsay; William Kerr

doi:10.1039/D3SC01337E

Experimental and computational insights into the mechanism of the copper(I)-catalysed sulfonylative Suzuki-Miyaura reaction

Helen Sneddon^*, Callum Hall, Peter Pogany, David Lindsay, William Kerr^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

A mechanistic study into the copper(I)-catalysed sulfonylative Suzuki–Miyaura reaction, incorporating sulfur dioxide, is described. Utilising spectroscopic and computational techniques, an exploration into the individual components of the competing catalytic cycles is delineated, including identification of the resting state catalyst, transmetalation of arylboronic acid onto copper(I), the sulfur dioxide insertion process, and the oxidative addition of aryl halide to CuI. Studies also investigated prominent side-reactions which were uncovered, including a competing copper(II)-catalysed mechanism. This led to an additional proposed and connected CuI/CuII/CuIII catalytic cycle to account for by-product formation.

Original language	English
Pages (from-to)	6738-6755
Number of pages	18
Journal	Chemical Science
Volume	14
DOIs	https://doi.org/10.1039/D3SC01337E
Publication status	Published - 31 May 2023

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10.1039/D3SC01337ELicence: CC BY

Experimental and computational insights into the mechanism of the copper(I)-catalysed sulfonylative Suzuki–Miyaura reaction
© 2023 The Author(s)
Final published version, 3.08 MBLicence: CC BY

Cite this

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abstract = "A mechanistic study into the copper(I)-catalysed sulfonylative Suzuki–Miyaura reaction, incorporating sulfur dioxide, is described. Utilising spectroscopic and computational techniques, an exploration into the individual components of the competing catalytic cycles is delineated, including identification of the resting state catalyst, transmetalation of arylboronic acid onto copper(I), the sulfur dioxide insertion process, and the oxidative addition of aryl halide to CuI. Studies also investigated prominent side-reactions which were uncovered, including a competing copper(II)-catalysed mechanism. This led to an additional proposed and connected CuI/CuII/CuIII catalytic cycle to account for by-product formation.",

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T1 - Experimental and computational insights into the mechanism of the copper(I)-catalysed sulfonylative Suzuki-Miyaura reaction

AU - Sneddon, Helen

AU - Hall, Callum

AU - Pogany, Peter

AU - Lindsay, David

AU - Kerr, William

PY - 2023/5/31

Y1 - 2023/5/31

N2 - A mechanistic study into the copper(I)-catalysed sulfonylative Suzuki–Miyaura reaction, incorporating sulfur dioxide, is described. Utilising spectroscopic and computational techniques, an exploration into the individual components of the competing catalytic cycles is delineated, including identification of the resting state catalyst, transmetalation of arylboronic acid onto copper(I), the sulfur dioxide insertion process, and the oxidative addition of aryl halide to CuI. Studies also investigated prominent side-reactions which were uncovered, including a competing copper(II)-catalysed mechanism. This led to an additional proposed and connected CuI/CuII/CuIII catalytic cycle to account for by-product formation.

AB - A mechanistic study into the copper(I)-catalysed sulfonylative Suzuki–Miyaura reaction, incorporating sulfur dioxide, is described. Utilising spectroscopic and computational techniques, an exploration into the individual components of the competing catalytic cycles is delineated, including identification of the resting state catalyst, transmetalation of arylboronic acid onto copper(I), the sulfur dioxide insertion process, and the oxidative addition of aryl halide to CuI. Studies also investigated prominent side-reactions which were uncovered, including a competing copper(II)-catalysed mechanism. This led to an additional proposed and connected CuI/CuII/CuIII catalytic cycle to account for by-product formation.

U2 - 10.1039/D3SC01337E

DO - 10.1039/D3SC01337E

M3 - Article

SN - 2041-6520

VL - 14

SP - 6738

EP - 6755

JO - Chemical Science

JF - Chemical Science

ER -