Enantioselective cyclopropanation and C-H insertion reactions of α-substituted vinyl ketones with α-diazoesters have been accomplished using a N,N'-dioxide-scandium(iii) complex catalyst. Various tetrasubstituted cyclopropanes and E-enone derivatives bearing a chiral ester substituent were obtained simultaneously with good yields and excellent enantioselectivities.

An efficient asymmetric intramolecular trapping of ammonium ylides of α-diazoketones with enones to synthesize indoline derivatives was realized. A Rh(II)/chiral N,N'-dioxide-Sc(III) complex bimetallic relay catalytic system was established. A series of optically active 2,2,3-trisubstituted indolines were obtained in high yields (up to 99%), good enantioselectivities (up to 99% ee), and excellent diastereoselectivities (up to >19:1 dr) under mild reaction conditions.

An easily available L-proline-derived guanidine-amide was found efficient to catalyze [4+2] cycloaddition of azlactones with 2-benzothiazolimines, affording various benzothiazolopyrimidines bearing adjacent tertiary and quaternary stereogenic centers in excellent results at...

We reported an efficient asymmetric amination of azlactones with N-aryl-N-aroyldiazenes through a chiral N,Nʹ-dioxide-based Lewis acid catalyst. The multicoordination ability of Nd(III) enabled it to simutaneously activate and to locate...