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Visible-Light-Induced, Copper-Catalyzed Three-Component Coupling of Alkyl Halides, Olefins, and Trifluoromethylthiolate to Generate Trifluoromethyl Thioethers

He, Jian and Chen, Caiyou and Fu, Gregory C. and Peters, Jonas C. (2018) Visible-Light-Induced, Copper-Catalyzed Three-Component Coupling of Alkyl Halides, Olefins, and Trifluoromethylthiolate to Generate Trifluoromethyl Thioethers. ACS Catalysis, 8 (12). pp. 11741-11748. ISSN 2155-5435. PMCID PMC6687088. https://resolver.caltech.edu/CaltechAUTHORS:20181031-131746669

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Abstract

Photoinduced, copper-catalyzed coupling reactions are emerging as a powerful method for generating Csp^3–Y (Y = C or heteroatom) bonds from alkyl electrophiles and nucleophiles. Corresponding three-component couplings of alkyl electrophiles, olefins, and nucleophiles have the potential to generate an additional Csp3–Y bond and to efficiently add functional groups to both carbons of an olefin, which serves as a readily available linchpin. In this report, we establish that a variety of electrophiles and a trifluoromethylthiolate nucleophile can add across an array of olefins (including styrenes and electron-poor olefins) in the presence of CuI/binap and blue-LED irradiation, thereby generating trifluoromethyl thioethers in good yield. The process tolerates a wide range of functional groups, and an initial survey of other nucleophiles (i.e., bromide, cyanide, and azide) suggests that this three-component coupling strategy is versatile. Mechanistic studies are consistent with a photoexcited Cu(I)/binap/SCF_3 complex serving as a reductant to generate an alkyl radical from the electrophile, which likely reacts in turn with the olefin and a Cu(II)/SCF_3 complex to afford the coupling product.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acscatal.8b04094DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/acscatal.8b04094PublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6687088PubMed CentralArticle
ORCID:
AuthorORCID
He, Jian0000-0002-3388-3239
Fu, Gregory C.0000-0002-0927-680X
Peters, Jonas C.0000-0002-6610-4414
Additional Information:© 2018 American Chemical Society. Received: October 10, 2018; Revised: October 24, 2018; Published: October 31, 2018. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences, Grant R01-109194). We are also grateful to the Dow Next Generation Educator Fund. We thank Dr. Tanvi S. Ratani, Dr. Paul H. Oyala (Caltech EPR Facility, supported by NSF-1531940), Larry M. Henling, Dr. Jun Myun Ahn, and Theodore M. Donnell for experimental assistance and for helpful discussions. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NIHR01-109194
NSFCHE-1531940
Subject Keywords:copper catalysis, C–S bond formation, three-component cross-coupling, photoredox catalysis, photochemistry
Issue or Number:12
PubMed Central ID:PMC6687088
Record Number:CaltechAUTHORS:20181031-131746669
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20181031-131746669
Official Citation:Visible-Light-Induced, Copper-Catalyzed Three-Component Coupling of Alkyl Halides, Olefins, and Trifluoromethylthiolate To Generate Trifluoromethyl Thioethers. Jian He, Caiyou Chen, Gregory C. Fu, and Jonas C. Peters. ACS Catalysis 2018 8 (12), 11741-11748. DOI: 10.1021/acscatal.8b04094
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:90547
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:31 Oct 2018 21:06
Last Modified:28 Feb 2020 17:01

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