期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 139, 期 49, 页码 18101-18106出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b10907
关键词
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资金
- 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
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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