The chemistry of a-diazocarbonyl compounds has attracted great attention because of its extensive applications in organic chemistry.1 However, the utility of the nucleophilic capability of a-diazoester has been less studied. Using chiral N,N'-dioxide-scandium(III) complexes, we have systematic studied the catalytic asymmetric reactions of a-diazoesters with carbonyl compounds. First, using 0.05 mol % chiral N,N'-dioxide-scandium(III) complex, we have achieved the ?rst catalytic enantioselective Roskamp reaction of a-alkyl-a-diazoesters with aromatic aldehydes (figure, A).2 Then, a-diazoesters were discovered to be good electrophiles in a catalytic asymmetric a-functionalization of ketones for the ?rst time (figure, B).3 We also developed the first catalytic asymmetric ring-expansion reaction of isatins and a-diazoesters providing highly functionalized C4-quaternary 2-quinolones in high yields and ee values in the presence of 0.05�0.5 mol% of catalyst (figure, C).4 Reference (1) Ye, T.; Mckervey, M. A. Chem. Rev. 1994  , 94, 1091.(2) Li, W.; Wang, J.; Hu, X.; Shen, K.; Wang, W.; Chu, Y.; Lin, L.; Liu, X.; Feng, X. M. J. Am. Chem. Soc. 2010  , 132, 8532.(3) Li, W.; Liu, X.; Hao, X.; Hu, X.; Chu, Y.; Cao, W.; Song, Q.; Hu, C.; Lin, L.; Feng, X. M. J. Am. Chem. Soc. 2011  , 133, 15268.(4) Li, W.; Liu, X.; Hao, X.; Cai, Y.; Lin, L.; Feng, X. M. Angew. Chem., Int. Ed. 2012  , 51, 8644.

Catalytic asymmetric new reactions of alfa-diazoesters with carbonyl compounds catalyzed by chiral <i>N,N</i>'-dioxide-scandium(III) complexes

246th National Meeting (2013)

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Catalytic asymmetric new reactions of alfa-diazoesters with carbonyl compounds catalyzed by chiral N,N'-dioxide-scandium(III) complexes