Combining Sanford arylations on benzodiazepines with the nuisance effect

Khan, Raysa, Boonseng, Sarote, Kemmitt, Paul, 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 and Catalysis, 359 (18). pp. 3261-3269. ISSN 1615-4150

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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.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Subjects: Q Science > QD Chemistry > QD0146 Inorganic chemistry
Q Science > QD Chemistry > QD0241 Organic chemistry
Q Science > QD Chemistry > QD0241 Organic chemistry > QD0411 Organometallic chemistry and compounds
Depositing User: John Spencer
Date Deposited: 29 Jun 2017 14:40
Last Modified: 02 Oct 2017 09:22
URI: http://sro.sussex.ac.uk/id/eprint/68893

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A Precompetitive Modular Peptidomimetic Toolkit for Targeting PPIs iCASEG1436EPSRC-ENGINEERING & PHYSICAL SCIENCES RESEARCH COUNCILEP/M507568/1