Ruthenium-Catalyzed para-Selective C−H Alkylation of Aniline Derivatives

Jamie A. Leitch; Claire L. Mcmullin; Andrew J. Paterson; Mary F. Mahon; Yunas Bhonoah; Christopher G. Frost

doi:10.1002/anie.201708961

Ruthenium-Catalyzed para-Selective C−H Alkylation of Aniline Derivatives

Jamie A. Leitch, Claire L. Mcmullin, Andrew J. Paterson, Mary F. Mahon, Yunas Bhonoah, Christopher G. Frost

Syngenta Ltd

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Abstract

The para-selective C−H alkylation of aniline derivatives furnished with a pyrimidine auxiliary is herein reported. This reaction is proposed to take place via an N−H-activated cyclometalate formed in situ. Experimental and DFT mechanistic studies elucidate a dual role of the ruthenium catalyst. Here the ruthenium catalyst can undergo cyclometalation by N−H metalation (as opposed to C−H metalation in meta-selective processes) and form a redox active ruthenium species, to enable site-selective radical addition at the para position.

Original language	English
Pages (from-to)	15131-15135
Number of pages	6
Journal	Angewandte Chemie International Edition
Volume	56
Issue number	47
Early online date	2 Oct 2017
DOIs	https://doi.org/10.1002/anie.201708961
Publication status	Published - 20 Nov 2017

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This is the peer reviewed version of the following article: Leitch, JA, Mcmullin, CL, Paterson, AJ, Mahon, MF, Bhonoah, Y & Frost, CG 2017, 'Ruthenium-Catalyzed para-Selective C−H Alkylation of Aniline Derivatives' Angewandte Chemie-International Edition., which has been published in final form at https://doi.org/10.1002/anie.201708961. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.
Accepted author manuscript, 1.12 MB

Christopher Frost
- Department of Chemistry - Visiting Professor
Person: Honorary / Visiting Staff

Balena High Performance Computing (HPC) System
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High Performance Computing (HPC) Facility
Chapman, S. (Manager)
University of Bath
Facility/equipment: Facility
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Material and Chemical Characterisation (MC2)
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title = "Ruthenium-Catalyzed para-Selective C−H Alkylation of Aniline Derivatives",

abstract = "The para-selective C−H alkylation of aniline derivatives furnished with a pyrimidine auxiliary is herein reported. This reaction is proposed to take place via an N−H-activated cyclometalate formed in situ. Experimental and DFT mechanistic studies elucidate a dual role of the ruthenium catalyst. Here the ruthenium catalyst can undergo cyclometalation by N−H metalation (as opposed to C−H metalation in meta-selective processes) and form a redox active ruthenium species, to enable site-selective radical addition at the para position.",

author = "Leitch, {Jamie A.} and Mcmullin, {Claire L.} and Paterson, {Andrew J.} and Mahon, {Mary F.} and Yunas Bhonoah and Frost, {Christopher G.}",

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T1 - Ruthenium-Catalyzed para-Selective C−H Alkylation of Aniline Derivatives

AU - Leitch, Jamie A.

AU - Mcmullin, Claire L.

AU - Paterson, Andrew J.

AU - Mahon, Mary F.

AU - Bhonoah, Yunas

AU - Frost, Christopher G.

PY - 2017/11/20

Y1 - 2017/11/20

N2 - The para-selective C−H alkylation of aniline derivatives furnished with a pyrimidine auxiliary is herein reported. This reaction is proposed to take place via an N−H-activated cyclometalate formed in situ. Experimental and DFT mechanistic studies elucidate a dual role of the ruthenium catalyst. Here the ruthenium catalyst can undergo cyclometalation by N−H metalation (as opposed to C−H metalation in meta-selective processes) and form a redox active ruthenium species, to enable site-selective radical addition at the para position.

AB - The para-selective C−H alkylation of aniline derivatives furnished with a pyrimidine auxiliary is herein reported. This reaction is proposed to take place via an N−H-activated cyclometalate formed in situ. Experimental and DFT mechanistic studies elucidate a dual role of the ruthenium catalyst. Here the ruthenium catalyst can undergo cyclometalation by N−H metalation (as opposed to C−H metalation in meta-selective processes) and form a redox active ruthenium species, to enable site-selective radical addition at the para position.

U2 - 10.1002/anie.201708961

DO - 10.1002/anie.201708961

M3 - Article

SN - 1433-7851

VL - 56

SP - 15131

EP - 15135

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

IS - 47

ER -

Ruthenium-Catalyzed para-Selective C−H Alkylation of Aniline Derivatives

Abstract

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Christopher Frost

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Balena High Performance Computing (HPC) System

High Performance Computing (HPC) Facility

MC2- Nuclear Magnetic Resonance (NMR)

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