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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

Ahn, Jun Myun and Peters, Jonas C. and Fu, Gregory C. (2017) 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. Journal of the American Chemical Society, 139 (49). pp. 18101-18106. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20171205-074829551

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Abstract

Despite the long history of S_N2 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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.7b10907DOIArticle
http://pubs.acs.org/doi/10.1021/jacs.7b10907PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jacs.7b10907PublisherSupporting Information
ORCID:
AuthorORCID
Peters, Jonas C.0000-0002-6610-4414
Fu, Gregory C.0000-0002-0927-680X
Additional Information:© 2017 American Chemical Society. Received: October 12, 2017; Published: December 4, 2017. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences, grant R01-GM109194), the Natural Sciences and Engineering Research Council of Canada (graduate research fellowship for J.M.A.), the National Science Foundation (support of the Caltech EPR Facility (NSF-1531940)), and the Arnold and Mabel Beckman Foundation (support of the Beckman Institute Laser Resource Center). We thank Kareem I. Hannoun, Lawrence M. Henling, Dr. Brian C. Sanders, Dr. Jonas Schwaben, Dr. Michael K. Takase, and Dr. Haolin Yin for assistance and helpful discussions. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NIHR01-GM109194
Natural Sciences and Engineering Research Council of Canada (NSERC)UNSPECIFIED
NSFCHE-1531940
Arnold and Mabel Beckman FoundationUNSPECIFIED
Issue or Number:49
Record Number:CaltechAUTHORS:20171205-074829551
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20171205-074829551
Official Citation: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. Jun Myun Ahn, Jonas C. Peters, and Gregory C. Fu. Journal of the American Chemical Society 2017 139 (49), 18101-18106. DOI: 10.1021/jacs.7b10907
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:83684
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:08 Dec 2017 03:46
Last Modified:03 Oct 2019 19:09

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