A zinc/PyBisulidine catalyzed asymmetric Mannich reaction of N-tosyl imines with 3-acyloxy-2-oxindoles.

A Zn-PyBisulidine catalyzed asymmetric Mannich reaction of 3-acyloxy-2-oxindoles has been developed. Various quaternary substituted 3-acyloxy-2-oxindoles bearing vicinal amino alcohol motifs were obtained in good to excellent yields with moderate to excellent dr and excellent enantioselectivities. The utility of this reaction was demonstrated by the easy removal of the acyl group to give C3-hydroxy derivatives and their application as a key skeleton of the ligand for the Ni-catalyzed enantioselective Henry reaction.

Reversal of Enantioselectivity in the Copper-Aminophenol Sulfonamide Catalyzed Alkynylation of Isatins by Slightly Tuning the Ligand Structure and Basic Additives.

A series of new chiral aminophenol sulfonamide ligands with a monochiral arm has been developed for the first Cu(I) catalyzed enantiodivergent alkynylation of isatins. Dramatic reversal of enantioselectivity was accomplished by slightly tuning the substituted benzenesulfonamide and achiral basic additives. A wide range of both terminal alkynes and isatins are tolerated by this new catalyst system with up to 99% yield and 97% ee.

Development of TsDPEN based imine-containing ligands for the copper-catalysed asymmetric Kinugasa reaction.

A novel class of chiral N,N,N imine-containing ligands derived from TsDPEN (N-(p-tosyl)-1,2-diphenylethylene-1,2-diamine) has been developed and applied to the copper-catalyzed asymmetric Kinugasa reaction. The copper(ii) salt proved to be an efficient catalyst precursor, and it provides an efficient way to synthesize enantioenriched cis-ß-lactam. The pathway is air-tolerant and easily manipulated, and the ligands are easy to synthesize. A working model is proposed in which the stereocontrolling step is the [2 + 2] cycloaddition between ketene and imine to explain the observed stereoselectivities.