Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published November 4, 2015 | Accepted Version + Supplemental Material
Journal Article Open

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

Files

ja5b08452_si_001.pdf
Files (2.2 MB)
Name Size Download all
md5:0644c79bf5bde45a5e101c5247b41a5f
1.7 MB Preview Download
md5:5c95c29005736c9783448f5b515570b0
408.7 kB Preview Download

Additional details

Created:
August 20, 2023
Modified:
October 25, 2023