ChemRxiv
These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
1/1
3 files

Nickel-Catalyzed 1,2-Carboamination of Alkenyl Alcohols

preprint
submitted on 12.03.2021, 01:33 and posted on 16.03.2021, 10:50 by Taeho Kang, Nana Kim, Peter Cheng, Hao Zhang, Klement Foo, Keary Engle
An alcohol-directed, nickel-catalyzed three-component umpolung carboamination of unactivated alkenes with aryl/alkenylboronic esters and electrophilic aminating reagents is reported. This transformation is enabled by specifically tailored O-(2,6-dimethoxybenzoyl)hydroxylamine electrophiles that suppress competitive processes, including undesired β-hydride elimination and transesterification between the alcohol substrate and electrophile. The reaction delivers the desired 1,2-carboaminated products with excellent regio- and diastereoselectivity and exhibits a broad scope of coupling partners and alkenes, including complex natural products. Various mechanistic experiments and analysis of the stereochemical outcome with a cyclic alkene substrate, as confirmed by X-ray crystallographic analysis, support alcohol-directed syn-insertion of an organonickel(I) species.

Funding

NSF-CHE-1800280

Kwanjeong Educational Foundation

History

Email Address of Submitting Author

keary@scripps.edu

Institution

The Scripps Research Institute

Country

United States

ORCID For Submitting Author

0000-0003-2767-6556

Declaration of Conflict of Interest

No conflict of interest to declare.

Exports