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Nature. 2016 Nov 10;539(7628):272-275. doi: 10.1038/nature19810. Epub 2016 Oct 12.

Amide-directed photoredox-catalysed C-C bond formation at unactivated sp3 C-H bonds.

Author information

1
Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, USA.
2
Department of Chemistry, Columbia University, New York, New York 10027, USA.

Abstract

Carbon-carbon (C-C) bond formation is paramount in the synthesis of biologically relevant molecules, modern synthetic materials and commodity chemicals such as fuels and lubricants. Traditionally, the presence of a functional group is required at the site of C-C bond formation. Strategies that allow C-C bond formation at inert carbon-hydrogen (C-H) bonds enable access to molecules that would otherwise be inaccessible and the development of more efficient syntheses of complex molecules. Here we report a method for the formation of C-C bonds by directed cleavage of traditionally non-reactive C-H bonds and their subsequent coupling with readily available alkenes. Our methodology allows for amide-directed selective C-C bond formation at unactivated sp3 C-H bonds in molecules that contain many such bonds that are seemingly indistinguishable. Selectivity arises through a relayed photoredox-catalysed oxidation of a nitrogen-hydrogen bond. We anticipate that our findings will serve as a starting point for functionalization at inert C-H bonds through a strategy involving hydrogen-atom transfer.

PMID:
27732580
PMCID:
PMC5574171
DOI:
10.1038/nature19810
[Indexed for MEDLINE]
Free PMC Article

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