화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.137, No.27, 8700-8703, 2015
Catalytic Asymmetric Arylation of alpha-Aryl-alpha-diazoacetates with Aniline Derivatives
The asymmetric arylation of diazo compounds with aniline derivatives cooperatively catalyzed by an achiral dirhodium complex and a chiral spiro phosphoric acid is reported. The reaction provides a new method for the facile synthesis of a-diarylacetates, versatile building blocks with alpha-diaryl tertiary chiral center, in good yields (up to 95%) with high enantioselectivities (up to 97% ee). Preliminary mechanistic studies suggest that the arylation reaction proceeds via a stepwise process, in which the enantioselectivity is controlled by a chiral spiro phosphoric acid-promoted proton shift in a zwitterionic intermediate. This work represents the first asymmetric intermolecular C(sp(2))-H bond insertion reaction with arenes.