A series of A-B type sterically regular bicyclio[3.3.0] diene-based polymers were designed and synthesized as immobilized chiral diene ligands for asymmetric catalysis. With polymeric diene 6b, good to excellent enantioselectivities can be achieved in Rh-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated ketones.

The use of unsymmetrical vicinal diamines as ligands for Ru-catalyzed asymmetric transfer hydrogenation is described. With a SmI₂-mediated cross-coupling protocol, a series of enantiomerically pure unsymmetrical vicinal diamines were readily prepared and examined in the asymmetric transfer hydrogenation. It was found that an aromatic substituent on the carbon bearing the –NHTs group and a bulky alkyl substituent on the other side, are both very important for the effectiveness of the ligand, suggesting that the substituent has a dramatic effect on the catalyst efficiency. With ligand 8, excellent enantioselectivities that are comparable to N-tosyl-1,2-diphenylethane-1,2-diamine (TsDPEN) were achieved. The results provide some helpful information on the mechanism of Ru-catalyzed asymmetric transfer hydrogenation.

An efficient and practical asymmetric synthesis of highly enantiomerically enriched α-allenylglycines by room temperature indium-mediated allenylation of chiral N-tert-butanesulfinyl imino esters with propargylic halides is described. The synthetic utilities of the approach were demonstrated by the rapid and convenient preparation of challenging cis-substituted proline derivatives.

A new and efficient protocol for straightforward synthesis of chromeno[3,4-b]pyrrol-4(3H)-one derivatives by palladium-catalyzed sequential coupling/cyclization reactions has been developed. The key strategy relies on creation of pyrrole ring through palladium-catalyzed intramolecular hydroamination of related acetylenic aminocoumarins. The synthetic utility of the obtained chromeno[3,4-b]pyrrol-4(3H)-one product has been demonstrated by the expedient synthesis of polycyclic lamellarin scaffold in four steps. It provides a new entry to synthesis of potentially valuable lamellarin analogues.

The asymmetric alkynylation of aldehydes catalyzed by bifunctional Zn(salen) catalyst was realized. With a Kozlowski salen ligand (7e) bearing secondary basic 1-piperidinylmethyl groups at C-3 and C-3′, the enhanced catalytic reactivity and stereoselectivity in comparison with that of normal salen ligands in the alkynylzinc addition to aldehydes were observed.