Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 139, Issue 49, Pages 18101-18106Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b10907
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Funding
- National Institutes of Health (National Institute of General Medical Sciences) [R01-GM109194]
- Natural Sciences and Engineering Research Council of Canada
- National Science Foundation [NSF-1531940]
- Arnold and Mabel Beckman Foundation
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1531940] Funding Source: National Science Foundation
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Despite the long history of S(N)2 reactions between nitrogen nucleophiles and alkyl electrophiles, many such substitution reactions remain out of reach. In recent years, efforts to develop transition-metal catalysts to address this deficiency have begun to emerge. In this report, we address the challenge of coupling a carbamate nucleophile with an unactivated secondary alkyl electrophile to generate a substituted carbamate, a process that has not been achieved effectively in the absence of a catalyst; the product carbamates can serve as useful intermediates in organic synthesis as well as bioactive compounds in their own right. Through the design and synthesis of a new copper-based photoredox catalyst, bearing a tridentate carbazolide/bisphosphine ligand, that can be activated upon irradiation by blue-LED lamps, we can achieve the coupling of a range of primary carbamates with unactivated secondary alkyl bromides at room temperature. Our mechanistic observations are consistent with the new copper complex serving its intended role as a photoredox catalyst, working in conjunction with a second copper complex that mediates C-N bond formation in an out-of-cage process.
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