Cobalt-catalyzed Wagner–Meerwein rearrangements with concomitant nucleophilic hydrofluorination

Reece  H. Hoogesteger; Nicola Murdoch; David  B. Cordes; Craig  Paterson Johnston

doi:10.1002/anie.202308048

Cobalt-catalyzed Wagner–Meerwein rearrangements with concomitant nucleophilic hydrofluorination

Reece H. Hoogesteger, Nicola Murdoch, David B. Cordes, Craig Paterson Johnston^*

^*Corresponding author for this work

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

Abstract

We report a cobalt-catalyzed Wagner-Meerwein rearrangement of gem-disubstituted allylarenes that generates fluoroalkane products with isolated yields up to 84%. Modification of the counteranion of the N-fluoropyridinium oxidant suggests the substrates undergo nucleophilic fluorination during the reaction. Subjecting the substrates to other known metal-mediated hydrofluorination procedures did not lead to observable 1,2-aryl migration. Thus, indicating the unique ability of these cobalt-catalyzed conditions to generate a sufficiently reactive electrophilic intermediate capable of promoting this Wagner-Meerwein rearrangement.

Original language	English
Article number	e202308048
Number of pages	7
Journal	Angewandte Chemie International Edition
Volume	62
Issue number	35
Early online date	19 Jul 2023
DOIs	https://doi.org/10.1002/anie.202308048
Publication status	Published - 28 Aug 2023

Keywords

Cobalt catalysis
Hydrofluorination
Wagner-Meerwein
Cations
Phenonium Ion

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10.1002/anie.202308048Licence: CC BY

Hoogesteger_2023_ACIE_Cobalt‐Catalyzed_CC
Copyright © 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Final published version, 8.35 MBLicence: CC BY

RS URF 2018 Craig Johnston: Enantioselective radical reactions facilitated by ion-bindong catalysis
Johnston, C. P. (PI)
1/10/18 → 30/09/23
Project: Fellowship
C Johnston Enchancement Award: Chiral Organic Bifunctional Electron-Transfer Catalysts
Johnston, C. P. (PI)
The Royal Society
1/10/18 → 30/09/22
Project: Standard

Cobalt-Catalysed Hydrofunctionalisation of Alkenes (Thesis Data)
Hoogesteger, R. H. (Creator) & Johnston, C. P. (Supervisor), University of St Andrews, 11 May 2029
DOI: 10.17630/f3b089f1-f40f-4565-926f-36207e3a919a
Dataset: Thesis dataset
Cobalt-Catalyzed Wagner–Meerwein Rearrangements with Concomitant Nucleophilic Hydrofluorination (dataset)
Johnston, C. P. (Creator), Hoogesteger, R. H. (Owner), Murdoch, N. (Owner) & Cordes, D. B. (Contributor), University of St Andrews, 7 Jul 2023
DOI: 10.17630/5944443f-21ce-4570-95c4-ee55c518f9c1
Dataset

File
CCDC 2265708: Experimental Crystal Structure Determination
Hoogesteger, R. H. (Creator), Murdoch, N. (Creator), Cordes, D. B. (Creator) & Johnston, C. P. (Creator), Cambridge Crystallographic Data Centre, 2023
DOI: 10.5517/ccdc.csd.cc2g1nck, https://doi.org/10.17630/sta/909
Dataset

Cite this

@article{372c442ec6fe4eae91037e6fc746f48c,

title = "Cobalt-catalyzed Wagner–Meerwein rearrangements with concomitant nucleophilic hydrofluorination",

abstract = "We report a cobalt-catalyzed Wagner-Meerwein rearrangement of gem-disubstituted allylarenes that generates fluoroalkane products with isolated yields up to 84%. Modification of the counteranion of the N-fluoropyridinium oxidant suggests the substrates undergo nucleophilic fluorination during the reaction. Subjecting the substrates to other known metal-mediated hydrofluorination procedures did not lead to observable 1,2-aryl migration. Thus, indicating the unique ability of these cobalt-catalyzed conditions to generate a sufficiently reactive electrophilic intermediate capable of promoting this Wagner-Meerwein rearrangement.",

keywords = "Cobalt catalysis, Hydrofluorination, Wagner-Meerwein, Cations, Phenonium Ion",

author = "Hoogesteger, {Reece H.} and Nicola Murdoch and Cordes, {David B.} and Johnston, {Craig Paterson}",

note = "Funding: The authors acknowledge funding from the Royal Society (University Research Fellowship URF\R1\180017 (CPJ) and associated Enhancement Award RGF\EA\181022 (CPJ and RHH)), and the EaSI-CAT Centre for Doctoral Training (RHH and NM).",

year = "2023",

month = aug,

day = "28",

doi = "10.1002/anie.202308048",

language = "English",

volume = "62",

journal = "Angewandte Chemie International Edition",

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number = "35",

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T1 - Cobalt-catalyzed Wagner–Meerwein rearrangements with concomitant nucleophilic hydrofluorination

AU - Hoogesteger, Reece H.

AU - Murdoch, Nicola

AU - Cordes, David B.

AU - Johnston, Craig Paterson

N1 - Funding: The authors acknowledge funding from the Royal Society (University Research Fellowship URF\R1\180017 (CPJ) and associated Enhancement Award RGF\EA\181022 (CPJ and RHH)), and the EaSI-CAT Centre for Doctoral Training (RHH and NM).

PY - 2023/8/28

Y1 - 2023/8/28

N2 - We report a cobalt-catalyzed Wagner-Meerwein rearrangement of gem-disubstituted allylarenes that generates fluoroalkane products with isolated yields up to 84%. Modification of the counteranion of the N-fluoropyridinium oxidant suggests the substrates undergo nucleophilic fluorination during the reaction. Subjecting the substrates to other known metal-mediated hydrofluorination procedures did not lead to observable 1,2-aryl migration. Thus, indicating the unique ability of these cobalt-catalyzed conditions to generate a sufficiently reactive electrophilic intermediate capable of promoting this Wagner-Meerwein rearrangement.

AB - We report a cobalt-catalyzed Wagner-Meerwein rearrangement of gem-disubstituted allylarenes that generates fluoroalkane products with isolated yields up to 84%. Modification of the counteranion of the N-fluoropyridinium oxidant suggests the substrates undergo nucleophilic fluorination during the reaction. Subjecting the substrates to other known metal-mediated hydrofluorination procedures did not lead to observable 1,2-aryl migration. Thus, indicating the unique ability of these cobalt-catalyzed conditions to generate a sufficiently reactive electrophilic intermediate capable of promoting this Wagner-Meerwein rearrangement.

KW - Cobalt catalysis

KW - Hydrofluorination

KW - Wagner-Meerwein

KW - Cations

KW - Phenonium Ion

U2 - 10.1002/anie.202308048

DO - 10.1002/anie.202308048

M3 - Article

SN - 1433-7851

VL - 62

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

IS - 35

M1 - e202308048

ER -

Cobalt-catalyzed Wagner–Meerwein rearrangements with concomitant nucleophilic hydrofluorination

Abstract

Keywords

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Projects

RS URF 2018 Craig Johnston: Enantioselective radical reactions facilitated by ion-bindong catalysis

C Johnston Enchancement Award: Chiral Organic Bifunctional Electron-Transfer Catalysts

Datasets

Cobalt-Catalysed Hydrofunctionalisation of Alkenes (Thesis Data)

Cobalt-Catalyzed Wagner–Meerwein Rearrangements with Concomitant Nucleophilic Hydrofluorination (dataset)

CCDC 2265708: Experimental Crystal Structure Determination

Cite this