4.8 Article

Design of a Photoredox Catalyst that Enables the Direct Synthesis of Carbamate-Protected Primary Amines via Photoinduced, Copper-Catalyzed N-Alkylation Reactions of Unactivated Secondary Halides

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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 139, 期 49, 页码 18101-18106

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AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b10907

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资金

  1. National Institutes of Health (National Institute of General Medical Sciences) [R01-GM109194]
  2. Natural Sciences and Engineering Research Council of Canada
  3. National Science Foundation [NSF-1531940]
  4. Arnold and Mabel Beckman Foundation
  5. Division Of Chemistry
  6. 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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