Mechanism of Cu-catalyzed iododeboronation: a description of ligand-enabled transmetalation, disproportionation, and turnover in Cu-mediated oxidative coupling reactions

Matthew Andrews; Ambre Charpentier; Alexandra Martha Zoya Slawin; David Bradford Cordes; Stuart Macgregor; Allan John Bell Watson

doi:10.1021/acscatal.3c02839

Mechanism of Cu-catalyzed iododeboronation: a description of ligand-enabled transmetalation, disproportionation, and turnover in Cu-mediated oxidative coupling reactions

Matthew Andrews, Ambre Charpentier, Alexandra Martha Zoya Slawin, David Bradford Cordes, Stuart Macgregor^*, Allan John Bell Watson^*

^*Corresponding author for this work

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

Abstract

We report a combined experimental and computational study of the mechanism of the Cu-catalyzed arylboronic acid iododeboronation reaction. A combination of structural and density functional theory (DFT) analyses has allowed determination of the identity of the reaction precatalyst with insight into each step of the catalytic cycle. Key findings include a rationale for ligand (phen) stoichiometry related to key turnover events─the ligand facilitates transmetalation via H-bonding to an organoboron boronate generated in situ and phen loss/gain is integral to the key oxidative events. These data provide a framework for understanding ligand effects on these key mechanistic processes, which underpin several classes of Cu-mediated oxidative coupling reactions.

Original language	English
Pages (from-to)	11117-11126
Number of pages	10
Journal	ACS Catalysis
Volume	13
Issue number	16
Early online date	7 Aug 2023
DOIs	https://doi.org/10.1021/acscatal.3c02839
Publication status	Published - 18 Aug 2023

Keywords

Cu-catalyzed iododeboronation
DFT analysis
Cu-mediated oxidative coupling reactions

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Andrews_2023_ACS-C_Mechanism-Cu-catalyzed_CC
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Allan Watson Programme Grant: Boron: Beyond the Reagent
Watson, A. J. B. (PI), Morris, R. E. (CoI), Smith, A. D. (CoI) & Zysman-Colman, E. (CoI)
UK Research and Innovation
1/05/23 → 30/04/28
Project: Standard
A biochemical boron tagging stategy: A biochemical boron tagging strategy for biomolecule visualisation and profiling
Watson, A. J. B. (PI)
The Leverhulme Trust
1/09/22 → 31/08/24
Project: Fellowship
Accessing Pharmacophoric Space: Accessing Pharmacophoric Space Via Asymmetric Protonation
Watson, A. J. B. (PI)
EPSRC
1/10/19 → 30/09/22
Project: Standard

Dataset underpinning "Mechanism of Cu-catalyzed iododeboronation: A description of ligand-enabled transmetalation, disproportionation, and turnover in Cu-mediated oxidative coupling reactions"
Watson, A. J. B. (Creator), University of St Andrews, 11 Aug 2023
DOI: 10.17630/8603890e-da81-4225-9343-a3f5baba470c
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title = "Mechanism of Cu-catalyzed iododeboronation: a description of ligand-enabled transmetalation, disproportionation, and turnover in Cu-mediated oxidative coupling reactions",

abstract = "We report a combined experimental and computational study of the mechanism of the Cu-catalyzed arylboronic acid iododeboronation reaction. A combination of structural and density functional theory (DFT) analyses has allowed determination of the identity of the reaction precatalyst with insight into each step of the catalytic cycle. Key findings include a rationale for ligand (phen) stoichiometry related to key turnover events─the ligand facilitates transmetalation via H-bonding to an organoboron boronate generated in situ and phen loss/gain is integral to the key oxidative events. These data provide a framework for understanding ligand effects on these key mechanistic processes, which underpin several classes of Cu-mediated oxidative coupling reactions.",

keywords = "Cu-catalyzed iododeboronation, DFT analysis, Cu-mediated oxidative coupling reactions",

author = "Matthew Andrews and Ambre Charpentier and Slawin, {Alexandra Martha Zoya} and Cordes, {David Bradford} and Stuart Macgregor and Watson, {Allan John Bell}",

note = "Funding: Biotechnology and Biological Sciences Research Council - BB/R013780/; Engineering and Physical Sciences Research Council - EP/R025754/1, EP/W007517/1, EP/S027165/1; Leverhulme Trust - RF-2022-014.",

year = "2023",

month = aug,

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doi = "10.1021/acscatal.3c02839",

language = "English",

volume = "13",

pages = "11117--11126",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society (ACS)",

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Mechanism of Cu-catalyzed iododeboronation: a description of ligand-enabled transmetalation, disproportionation, and turnover in Cu-mediated oxidative coupling reactions. / Andrews, Matthew; Charpentier, Ambre; Slawin, Alexandra Martha Zoya et al.
In: ACS Catalysis, Vol. 13, No. 16, 18.08.2023, p. 11117-11126.

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

TY - JOUR

T1 - Mechanism of Cu-catalyzed iododeboronation

T2 - a description of ligand-enabled transmetalation, disproportionation, and turnover in Cu-mediated oxidative coupling reactions

AU - Andrews, Matthew

AU - Charpentier, Ambre

AU - Slawin, Alexandra Martha Zoya

AU - Cordes, David Bradford

AU - Macgregor, Stuart

AU - Watson, Allan John Bell

N1 - Funding: Biotechnology and Biological Sciences Research Council - BB/R013780/; Engineering and Physical Sciences Research Council - EP/R025754/1, EP/W007517/1, EP/S027165/1; Leverhulme Trust - RF-2022-014.

PY - 2023/8/18

Y1 - 2023/8/18

N2 - We report a combined experimental and computational study of the mechanism of the Cu-catalyzed arylboronic acid iododeboronation reaction. A combination of structural and density functional theory (DFT) analyses has allowed determination of the identity of the reaction precatalyst with insight into each step of the catalytic cycle. Key findings include a rationale for ligand (phen) stoichiometry related to key turnover events─the ligand facilitates transmetalation via H-bonding to an organoboron boronate generated in situ and phen loss/gain is integral to the key oxidative events. These data provide a framework for understanding ligand effects on these key mechanistic processes, which underpin several classes of Cu-mediated oxidative coupling reactions.

AB - We report a combined experimental and computational study of the mechanism of the Cu-catalyzed arylboronic acid iododeboronation reaction. A combination of structural and density functional theory (DFT) analyses has allowed determination of the identity of the reaction precatalyst with insight into each step of the catalytic cycle. Key findings include a rationale for ligand (phen) stoichiometry related to key turnover events─the ligand facilitates transmetalation via H-bonding to an organoboron boronate generated in situ and phen loss/gain is integral to the key oxidative events. These data provide a framework for understanding ligand effects on these key mechanistic processes, which underpin several classes of Cu-mediated oxidative coupling reactions.

KW - Cu-catalyzed iododeboronation

KW - DFT analysis

KW - Cu-mediated oxidative coupling reactions

U2 - 10.1021/acscatal.3c02839

DO - 10.1021/acscatal.3c02839

M3 - Article

C2 - 37614524

SN - 2155-5435

VL - 13

SP - 11117

EP - 11126

JO - ACS Catalysis

JF - ACS Catalysis

IS - 16

ER -

Mechanism of Cu-catalyzed iododeboronation: a description of ligand-enabled transmetalation, disproportionation, and turnover in Cu-mediated oxidative coupling reactions

Abstract

Keywords

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Projects

Allan Watson Programme Grant: Boron: Beyond the Reagent

A biochemical boron tagging stategy: A biochemical boron tagging strategy for biomolecule visualisation and profiling

Accessing Pharmacophoric Space: Accessing Pharmacophoric Space Via Asymmetric Protonation

Datasets

Dataset underpinning "Mechanism of Cu-catalyzed iododeboronation: A description of ligand-enabled transmetalation, disproportionation, and turnover in Cu-mediated oxidative coupling reactions"

Cite this