We report the synthesis of cobalt complexes of novel iminopyridine-oxazoline (IPO) ligands and their application to the asymmetric hydroboration of 1,1-disubstituted aryl alkenes. The new catalysts afforded α-alkyl-β-pinacolatoboranes with exclusive regioselectivity in high yields with up to 99.5% ee. Furthermore, we have applied this method to an efficient synthesis of naproxen.

A novel enantioselective copper-catalyzed intermolecular cyanotrifluoromethylation of alkenes has been developed, in which a variety of CF-containing alkylnitriles are furnished with excellent enantiomeric excess. Preliminary mechanistic studies revealed (1) the reaction was initiated by a SET process between activated Togni's CF reagent and a Cu(I) catalyst; (2) the released CF radical readily added to styrene to provide a benzylic radical, which was then trapped by a chiral Cu(II) cyanide species to deliver the desired alkylnitriles; (3) a low concentration of the CN anion was crucial to obtain high enantioselectivity.

We have developed a copper-catalyzed enantioselective intermolecular aminoarylation of alkenes using a novel N-fluoro-N-alkylsulfonamide as the amine reagent, which could react with the Cu(I) catalyst to release a related amino radical. After addition to styrene, the generated benzylic radical could couple with a chiral L*CuAr complex to achieve enantioselective arylation. Various optical 2,2-diarylethylamines were efficiently synthesized from simple styrenes with high enantioselectivity, and these products can serve as valuable synthons toward bioactive molecules' synthesis.

A novel asymmetric radical trifluoromethyl-arylation of alkenes has been developed, which provides an efficient approach to access chiral CF-containing 1,1-diarylmethane derivatives with good to excellent enantioselectivity. Various vinyl arenes and aryl boronic acids are compatible with these conditions. The utility of the method is demonstrated by accessing modified bioactive molecules.

A shorter path: A highly enantioselective bromocyclization of tryptamine has been developed using an anionic chiral phase-transfer catalyst. This method provides a direct approach for preparing chiral 3-bromopyrroloindoline from tryptamine, which enables a four-step enantioselective synthesis of (-)-chimonanthine. PG=protecting group.

A novel enantioselective copper-catalyzed trifluoromethylalkynylation of styrenes, proceeding through a radical relay process, is described herein, which affords structurally diverse CF-containing propargylic compounds in good yield with excellent enantioselectivities under very mild conditions. In addition, the reaction features wide substrate scope and good functional group tolerance. Moreover, the trifluoromethylalkynylated products can be easily converted into synthetically useful chiral terminal alkynes, allenes, Z-alkenes, as well as CF-modified nonsteroidal anti-inflammatory drugs.

The chiral iridium porphyrin [Ir((-)-D(4)-Por*)(Me)(EtOH)] displays excellent reactivity and stereoselectivity towards carbene insertion to C-H and Si-H bonds, affording corresponding products in high yields (up to 96%) and high enantioselectivities (up to 98% ee).

Chiral N-heterocyclic carbene catalyzed annulations of ynals and enals with 1,3-dicarbonyls have been described. The two reactions provided direct and efficient methods for enantioselective synthesis of functionalized dihydropyranones. Comparatively, the reactions starting from ynals were atom-economical; furthermore the reactions of enals demonstrated broader substrate compatibility.