Lin JS,
Li TT,
Liu J.-R,
Jiao G.-Y,
Gu Q.-S,
Cheng J.-T,
Guo Y.-L,
Hong X.
*
Liu X.-Y.
* Southern University of Science and Technology, Shenzhen and Zhejiang University,
Hangzhou, P. R. of China
Cu/Chiral Phosphoric Acid-Catalyzed Asymmetric Three-Component Radical-Initiated 1,2-Dicarbofunctionalization
of Alkenes.
J. Am. Chem. Soc. 2019;
141: 1074-1083
Key words
copper catalysis - chiral phosphoric acids
Significance
Owing to their ready availability, asymmetric dicarbofunctionalization of alkenes
remains an important topic in catalysis. The authors report a three-component asymmetric
difunctionalization of 1,1-disubstituted alkenes with a radical initiator and heteroaryl
nucleophile using copper and chiral phosphoric acid (CPA) catalyst.
Comment
The reaction proceeds through a Kharasch-type addition across the unactivated olefin,
whereupon the resultant tertiary radical undergoes a SET to form a tertiary cation.
The CPA’s H-bonding affects the facial selectivity of the attack of the indole moiety
in an asymmetric fashion to form the products.
