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‐ prod...

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Bibliographic Details
Published in:Advanced synthesis & catalysis Vol. 359; no. 18; pp. 3261 - 3269
Main Authors: 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, Spencer, John
Format: Journal Article
Language:English
Published: Germany Wiley Subscription Services, Inc 18-09-2017
John Wiley and Sons Inc
Subjects:
benzodiazepine
Benzodiazepines
C−H activation
DFT
Nuisance
palladacycle
Palladium
photocatalysis
Photoredox catalysis
Refluxing
Ruthenium
Update
Updates
DFT
C−H activation
palladacycle
photocatalysis
benzodiazepine
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Summary: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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ISSN:1615-4150
1615-4169
DOI:10.1002/adsc.201700626