Combining Sanford Arylations on Benzodiazepines with the Nuisance Effect
Combining Sanford Arylations on Benzodiazepines with the Nuisance Effect
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.
c-h activation, benzodiazepine, photocatalysis, palladacycle, DFT
Khan, Raysa
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Boonseng, Sarote
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Kemmitt, Paul D.
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Felix, Robert
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Coles, Simon J.
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Tizzard, Graham J.
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Williams, Gareth
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Simmonds, Olivia
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Harvey, Jessica-Lily
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Atack, John
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Cox, Hazel
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Spencer, John
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Khan, Raysa
ac317732-8e4c-4571-88b3-3b3f2372cec7
Boonseng, Sarote
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Kemmitt, Paul D.
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Felix, Robert
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Coles, Simon J.
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Tizzard, Graham J.
8474c0fa-40df-43a6-a662-7f3c4722dbf2
Williams, Gareth
41f1a889-82f4-4769-a5cb-4566c84658b4
Simmonds, Olivia
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Harvey, Jessica-Lily
441d2cc1-b04e-4cb9-8347-8fab935bfe38
Atack, John
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Cox, Hazel
334ee45b-6c64-4c3b-a3e0-2a72f342f2cf
Spencer, John
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Khan, Raysa, Boonseng, Sarote, Kemmitt, Paul D., Felix, Robert, Coles, Simon J., Tizzard, Graham J., Williams, Gareth, Simmonds, Olivia, Harvey, Jessica-Lily, Atack, John, Cox, Hazel and Spencer, John
(2017)
Combining Sanford Arylations on Benzodiazepines with the Nuisance Effect.
Advanced Synthesis & Catalysis.
(doi:10.1002/adsc.201700626).
Abstract
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.
Text
asc raysa paper 290617 for SRO
- Accepted Manuscript
More information
Accepted/In Press date: 29 June 2017
e-pub ahead of print date: 2 August 2017
Keywords:
c-h activation, benzodiazepine, photocatalysis, palladacycle, DFT
Identifiers
Local EPrints ID: 412137
URI: http://eprints.soton.ac.uk/id/eprint/412137
ISSN: 1615-4150
PURE UUID: 38e90925-b97e-41d4-be6d-6ae21229812f
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Date deposited: 11 Jul 2017 16:31
Last modified: 16 Mar 2024 05:31
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Contributors
Author:
Raysa Khan
Author:
Sarote Boonseng
Author:
Paul D. Kemmitt
Author:
Robert Felix
Author:
Gareth Williams
Author:
Olivia Simmonds
Author:
Jessica-Lily Harvey
Author:
John Atack
Author:
Hazel Cox
Author:
John Spencer
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