Turro, Raymond F. and Brandstätter, Marco and Reisman, Sarah E. (2022) Nickel‐Catalyzed Reductive Alkylation of Heteroaryl Imines. Angewandte Chemie International Edition . ISSN 1433-7851. doi:10.1002/anie.202207597. (In Press) https://resolver.caltech.edu/CaltechAUTHORS:20220721-9036000
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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.
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| 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. | |||||||||
| Group: | Heritage Medical Research Institute, Resnick Sustainability Institute | |||||||||
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| Subject Keywords: | imine alkylation; cross-electrophile coupling; nickel-catalyzed; electroreductive; redox non-innocent | |||||||||
| DOI: | 10.1002/anie.202207597 | |||||||||
| Record Number: | CaltechAUTHORS:20220721-9036000 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20220721-9036000 | |||||||||
| Official Citation: | Turro, R..F., Brandstätter, M. and Reisman, S..E. (2022), Nickel-Catalyzed Reductive Alkylation of Heteroaryl Imines. Angew. Chem. Int. Ed.. Accepted Author Manuscript. https://doi.org/10.1002/anie.202207597 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 115751 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | George Porter | |||||||||
| Deposited On: | 21 Jul 2022 19:52 | |||||||||
| Last Modified: | 21 Jul 2022 19:52 |
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