Nickel‐Catalyzed Reductive Alkylation of Heteroaryl Imines
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1.
California Institute of Technology
Abstract
A Ni-catalyzed reductive cross-coupling of heteroaryl imines with C(sp³) electrophiles for the preparation of heterobenzylic amines is reported. This umpolung-type alkylation proceeds under mild conditions, avoids the pre-generation of organometallic reagents, and exhibits good functional group tolerance. Mechanistic studies are consistent with the imine substrate acting as a redox-active ligand upon coordination to a low-valent Ni center. The resulting bis(2-imino)heterocycle·Ni complexes can engage in alkylation reactions with a variety of C(sp³) electrophiles, giving heterobenzylic amine products in good yields.
Additional Information
© 2022 Wiley-VCH GmbH. Accepted manuscript online: 05 July 2022. Manuscript accepted: 04 July 2022. Manuscript revised: 01 July 2022. Manuscript received: 23 May 2022. Dr. Scott Virgil and the Caltech Center for Catalysis and Chemical Synthesis are gratefully acknowledged for access to analytical equipment. Fellowship support was provided by the Swiss National Science Foundation (M. B.). S.E.R. is a Heritage Medical Research Institute Investigator and acknowledges financial support from the NIH (R35GM118191). The authors would also like to thank Dr. Nathan Dalleska and the Resnick Sustainability Institute's Water and Environmental Lab for elemental analysis of commercial manganese; Dr. Mona Shahgholi for assistance with mass spectrometry measurements; Dr. Paul Oyala for assistance with X-band EPR measurements; Dr. David E. Hill for invaluable assistance with electroanalytical and spectroelectrochemical experiments; as well as Z. Jaron Tong for helpful discussions on DFT calculations and non-innocent ligand complexes.Attached Files
Accepted Version - Angew_Chem_Int_Ed_-_2022_-_Turro_-_Nickel‐Catalyzed_Reductive_Alkylation_of_Heteroaryl_Imines.pdf
Supplemental Material - anie202207597-s1-2022-6-26_imineexp_si_combined.pdf
Files
Angew_Chem_Int_Ed_-_2022_-_Turro_-_Nickel‐Catalyzed_Reductive_Alkylation_of_Heteroaryl_Imines.pdf
Additional details
Identifiers
- Eprint ID
- 115751
- Resolver ID
- CaltechAUTHORS:20220721-9036000
- DOI
- 10.1002/anie.202207597
Related works
- Is new version of
- Discussion Paper: https://authors.library.caltech.edu/records/4wpcm-rkp48 (URL)
Funding
- Swiss National Science Foundation (SNSF)
- Heritage Medical Research Institute
- NIH
- R35GM118191
Dates
- Created
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2022-07-21Created from EPrint's datestamp field
- Updated
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2022-07-21Created from EPrint's last_modified field