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Adv Synth Catal - 2017 - Khan - Combining Sanford Arylations on Benzodiazepines with the Nuisance Effect.pdf (2.79 MB)

Combining Sanford arylations on benzodiazepines with the nuisance effect

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posted on 2023-06-21, 06:02 authored by Raysa Khan, Sarote Boonseng, Paul Kemmitt, Robert Felix, Simon J Coles, Graham J Tizzard, Gareth Williams, Olivia Simmonds, Jessica-Lily Harvey, John Atack, Hazel CoxHazel Cox, John SpencerJohn Spencer
5-Phenyl-1,3-dihydro-2H-1,4-benzodiazepin-2-ones react under palladium- and visible light photoredox catalysis, in refluxing methanol, with aryldiazonium salts to afford the respective 5-(2- arylphenyl) analogues. With 2- or 4-fluorobenzenediazonium derivatives, both fluoroaryl- and methoxyaryl- products were obtained, the latter resulting from a SNAr on the fluorobenzenediazonium salt (“nuisance effect”). A computational DFT analysis of the palladium-catalysed and the palladium/ruthenium-photocalysed mechanism for the functionalization of benzodiazepines indicated that in the presence of the photocatalyst the reaction proceeds via a low-energy SET pathway avoiding the high-energy oxidative addition step in the palladium-only catalysed reaction pathway.

Funding

A Precompetitive Modular Peptidomimetic Toolkit for Targeting PPIs iCASE; G1436; EPSRC-ENGINEERING & PHYSICAL SCIENCES RESEARCH COUNCIL; EP/M507568/1

History

Publication status

  • Published

File Version

  • Published version

Journal

Advanced Synthesis and Catalysis

ISSN

1615-4150

Publisher

Wiley

Issue

18

Volume

359

Page range

3261-3269

Department affiliated with

  • Chemistry Publications

Full text available

  • Yes

Peer reviewed?

  • Yes

Legacy Posted Date

2017-06-29

First Open Access (FOA) Date

2017-09-19

First Compliant Deposit (FCD) Date

2017-06-29

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