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Enantioselective Synthesis of N-Benzylic Heterocycles by Ni/Photoredox Dual Catalysis

Lacker, Caitlin R. and DeLano, Travis J. and Chen, Emily P. and Kong, Jongrock and Belyk, Kevin M. and Piou, Tiffany and Reisman, Sarah E. (2022) Enantioselective Synthesis of N-Benzylic Heterocycles by Ni/Photoredox Dual Catalysis. Journal of the American Chemical Society, 144 (44). pp. 20190-20195. ISSN 0002-7863. doi:10.1021/jacs.2c07917.

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An asymmetric cross-coupling of α-N-heterocyclic trifluoroborates with aryl bromides using Ni/photoredox dual catalysis has been developed. This C(sp²)–C(sp³) cross-coupling provides access to pharmaceutically relevant chiral N-benzylic heterocycles in good to excellent enantioselectivity when bioxazolines (BiOX) are used as the chiral ligand. High-throughput experimentation significantly streamlined reaction development by identifying BiOX ligands for further investigation and by allowing for rapid optimization of conditions for new trifluoroborate salts.

Item Type:Article
Related URLs:
URLURL TypeDescription
Lacker, Caitlin R.0000-0003-2531-2636
DeLano, Travis J.0000-0002-2052-611X
Chen, Emily P.0000-0002-6603-9886
Kong, Jongrock0000-0003-1509-687X
Belyk, Kevin M.0000-0003-1585-0430
Piou, Tiffany0000-0003-4923-9138
Reisman, Sarah E.0000-0001-8244-9300
Additional Information:Dr. Scott Virgil and the Caltech Center for Catalysis and Chemical Synthesis are gratefully acknowledged for access to analytical equipment. We thank Michael Takase for solving the structure of 5h and the Beckman Institute at Caltech and the Dow Next Generation Instrumentation Grant for support of the small molecule crystallography facility. Fellowship support was provided by the NSF (C.R.L., T.J.D., Grant No. DGE-1144469). S.E.R. acknowledges financial support from the NIH (R35GM118191). This work was supported by Merck Sharp & Dohme Corp., a subsidiary of Merck & Co., Inc., Kenilworth, NJ, USA. We thank Nelo R. Rivera, Wildredo Pinto, and Yongqian Zhang for providing analytical support in obtaining optical rotation, HRMS, and FT-IR characterization data for 5j. We thank Benjamin Sherry, Jamie McCabe Dunn, Louis-Charles Campeau, and Kevin Campos (all employees of Merck Sharp & Dohme Corp., a subsidiary of Merck & Co., Inc., Kenilworth, NJ, USA) for helpful discussions.
Funding AgencyGrant Number
Merck Sharp and DohmeUNSPECIFIED
NSF Graduate Research FellowshipDGE-1144469
Caltech Beckman InstituteUNSPECIFIED
Dow Next Generation Educator FundUNSPECIFIED
Issue or Number:44
Record Number:CaltechAUTHORS:20230125-514893900.20
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ID Code:118940
Deposited By: Research Services Depository
Deposited On:22 Feb 2023 19:29
Last Modified:22 Feb 2023 19:29

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