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Nickel-Catalyzed Reductive Alkylation of Heteroaryl Imines

Brandstätter, Marco and Turro, Raymond F. and Reisman, Sarah E. (2021) Nickel-Catalyzed Reductive Alkylation of Heteroaryl Imines. Cambridge University Press . (Unpublished) https://resolver.caltech.edu/CaltechAUTHORS:20210629-203340595

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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 ex-hibits good functional group tolerance. Mechanistic studies are consistent with the imine substrate acting as a redox-active ligand upon coordination to a low-valent nickel center. The resulting Ni-bis(2-imino)heterocycle complexes can engage in alkylation reactions with a variety of C(sp³) electrophiles, giving the heterobenzylic amine products in good yields.


Item Type:Report or Paper (Discussion Paper)
Related URLs:
URLURL TypeDescription
https://doi.org/10.33774/chemrxiv-2021-mdjf6DOIDiscussion Paper
ORCID:
AuthorORCID
Reisman, Sarah E.0000-0001-8244-9300
Additional Information:The content is available under CC BY NC ND 4.0 License. Jun 21, 2021 Version 1. 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 and Dirk Schild for assistance with X-band EPR measurements; as well as Z. Jaron Tong for helpful discussions on DFT calculations and non-innocent ligand complexes. The author(s) have declared they have no conflict of interest with regard to this content. The author(s) have declared ethics committee/IRB approval is not relevant to this content.
Group:Heritage Medical Research Institute, Resnick Sustainability Institute
Funders:
Funding AgencyGrant Number
Swiss National Science Foundation (SNSF)UNSPECIFIED
Heritage Medical Research InstituteUNSPECIFIED
NIHR35GM118191
Subject Keywords:Nickel-catalyzed; non-innocent ligand; imine alkylation; heterobenzylic amines; radical
Record Number:CaltechAUTHORS:20210629-203340595
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210629-203340595
Official Citation:Brandstätter M, Turro RF, Reisman S. Nickel-Catalyzed Reductive Alkylation of Heteroaryl Imines. ChemRxiv. Cambridge: Cambridge Open Engage; 2021; This content is a preprint and has not been peer-reviewed
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:109655
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:29 Jun 2021 22:33
Last Modified:29 Jun 2021 22:33

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