Photoinduced, Copper-Catalyzed Carbon–Carbon Bond Formation with Alkyl Electrophiles: Cyanation of Unactivated Secondary Alkyl Chlorides at Room Temperature
Abstract
We have recently reported that, in the presence of light and a copper catalyst, nitrogen nucleophiles such as carbazoles and primary amides undergo C–N coupling with alkyl halides under mild conditions. In the present study, we establish that photoinduced, copper-catalyzed alkylation can also be applied to C–C bond formation, specifically, that the cyanation of unactivated secondary alkyl chlorides can be achieved at room temperature to afford nitriles, an important class of target molecules. Thus, in the presence of an inexpensive copper catalyst (CuI; no ligand coadditive) and a readily available light source (UVC compact fluorescent light bulb), a wide array of alkyl halides undergo cyanation in good yield. Our initial mechanistic studies are consistent with the hypothesis that an excited state of [Cu(CN)_2]^− may play a role, via single electron transfer, in this process. This investigation provides a rare example of a transition metal-catalyzed cyanation of an alkyl halide, as well as the first illustrations of photoinduced, copper-catalyzed alkylation with either a carbon nucleophile or a secondary alkyl chloride.
Additional Information
© 2015 American Chemical Society. Received: August 10, 2015. Publication Date (Web): October 22, 2015. We thank Dr. Junwon Choi, Nathaniel T. Kadunce, Dr. Wesley Sattler, Dr. David VanderVelde, Dr. Scott C. Virgil, Paul Walton, and Dr. Daniel T. Ziegler for experimental assistance and for helpful discussions, and we thank the Gordon and Betty Moore Foundation, the National Science Foundation (graduate research fellowship to T.S.R.), and the NIH (NIGMS: R01 GM109194) for funding. T.S.R. and S.B. contributed equally to this work. The authors declare no competing financial interest.Attached Files
Accepted Version - nihms-739917.pdf
Supplemental Material - ja5b08452_si_001.pdf
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Additional details
- PMCID
- PMC4666296
- Eprint ID
- 61560
- Resolver ID
- CaltechAUTHORS:20151027-113729482
- Gordon and Betty Moore Foundation
- NSF Graduate Research Fellowship
- NIH
- R01 GM109194
- Created
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2015-10-27Created from EPrint's datestamp field
- Updated
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2022-05-19Created from EPrint's last_modified field