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Combining Sanford Arylations on Benzodiazepines with the Nuisance Effect

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
1615-4150
Khan, Raysa
ac317732-8e4c-4571-88b3-3b3f2372cec7
Boonseng, Sarote
83b6e024-fc9d-4f5f-9dc4-0e7c4c10d34f
Kemmitt, Paul D.
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Felix, Robert
acfd9272-cc4b-4838-bca1-8c31965d5a2e
Coles, Simon J.
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Tizzard, Graham J.
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Williams, Gareth
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Simmonds, Olivia
8f09d1ab-cfcc-47e9-a922-f9a35cbdf84e
Harvey, Jessica-Lily
441d2cc1-b04e-4cb9-8347-8fab935bfe38
Atack, John
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Cox, Hazel
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Spencer, John
a3cf55cd-a4c7-4af6-b16c-96c8fb8c4cf4
Khan, Raysa
ac317732-8e4c-4571-88b3-3b3f2372cec7
Boonseng, Sarote
83b6e024-fc9d-4f5f-9dc4-0e7c4c10d34f
Kemmitt, Paul D.
0f178e56-e8e2-4d3d-b8af-71d0f5641f19
Felix, Robert
acfd9272-cc4b-4838-bca1-8c31965d5a2e
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Tizzard, Graham J.
8474c0fa-40df-43a6-a662-7f3c4722dbf2
Williams, Gareth
41f1a889-82f4-4769-a5cb-4566c84658b4
Simmonds, Olivia
8f09d1ab-cfcc-47e9-a922-f9a35cbdf84e
Harvey, Jessica-Lily
441d2cc1-b04e-4cb9-8347-8fab935bfe38
Atack, John
126f23e8-97a6-4f79-badb-d40d5eae04fc
Cox, Hazel
334ee45b-6c64-4c3b-a3e0-2a72f342f2cf
Spencer, John
a3cf55cd-a4c7-4af6-b16c-96c8fb8c4cf4

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).

Record type: Article

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.

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asc raysa paper 290617 for SRO - Accepted Manuscript
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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: https://eprints.soton.ac.uk/id/eprint/412137
ISSN: 1615-4150
PURE UUID: 38e90925-b97e-41d4-be6d-6ae21229812f
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272
ORCID for Graham J. Tizzard: ORCID iD orcid.org/0000-0002-1577-5779

Catalogue record

Date deposited: 11 Jul 2017 16:31
Last modified: 14 Mar 2019 05:46

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