Issue 18, 2020

Metal-free reductive coupling of aliphatic aldehydes/ketones with 4-cyanopyridines: expanded scope and mechanistic studies

Abstract

An efficient and practical bis(pinacolato)diboron (B2pin2) mediated radical–radical cross-coupling of 4-cyanopyridine with aliphatic aldehydes/ketones has been established. The metal-free protocol features simple and mild reaction conditions and excellent functional group tolerance, and provides a general and convenient route to construct a wide range of pyridine-functionalized alcohols without transition-metal or organometallic reagents. The mechanistic studies offer significant insights into the key radical–radical coupling process between the pyridine-boryl radical and the ketyl radical, and the key radical cross-coupling intermediate was structurally characterized by NMR spectroscopy and X-ray diffraction, which is consistent with density functional theory calculations.

Graphical abstract: Metal-free reductive coupling of aliphatic aldehydes/ketones with 4-cyanopyridines: expanded scope and mechanistic studies

Supplementary files

Article information

Article type
Research Article
Submitted
12 Jul 2020
Accepted
22 Aug 2020
First published
24 Aug 2020

Org. Chem. Front., 2020,7, 2744-2751

Metal-free reductive coupling of aliphatic aldehydes/ketones with 4-cyanopyridines: expanded scope and mechanistic studies

L. Gao, G. Wang, H. Chen, J. Cao, X. Su, X. Liu, M. Yang, X. Cheng and S. Li, Org. Chem. Front., 2020, 7, 2744 DOI: 10.1039/D0QO00827C

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