Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 142, Issue 4, Pages 1966-1974Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.9b11423
Keywords
-
Categories
Funding
- JSPS KAKENHI [JP17H06451]
- Incentive Research Projects from RIKEN
- Fundamental Research Funds for the Central Universities [DUT18RC(3)002, DUT18GJ201]
Ask authors/readers for more resources
Integration of distinct substrate activation modes in a catalytic circle is critical for the development of new, powerful synthetic methodologies toward complex and value-added chemicals from simple and readily available feedstocks. Here, we describe a highly selective difunctionalization of imines through incorporation of activation of CO2 by intramolecular N/B Lewis pairs into a copper catalytic cycle. Experimental and computational studies on the mechanistic aspect revealed an alpha-borylalkylamido intermediate, a metal amide-based Lewis pair formed by borylation of a C-N double bond, and enabled an unprecedented CO2 fixation pattern that is in sharp contrast to the traditional CO2 insertion into transition-metal-element bonds. The unique lithium cyclic boracarbamate products could be easily transformed into multifunctional N-carboxylated alpha-amino boronates. The highly diastereoselective reactions of chiral N-tert-butanesulfinyl aldimines were also achieved. We hope that our findings may inspire further development of selective multicomponent reactions by incorporation of Lewis pair chemistry into transition-metal catalysis.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available