Min-Can Wang

Diastereomeric Aziridine Carbinol Catalyzed Enantioselective Arylation Reaction: Toward the Asymmetric Synthesis of Both Enantiomers of Chiral 3-Aryl Phthalide

The diastereomeric aziridine carbinols are applied, respectively, as efficient chiral ligand in the catalysis of asymmetric arylation and sequential arylation-lactonization cascade. The two diastereomers, which are facilely synthesized from the same chiral source, function as pseudo enantiomers in arylation of aromatic aldehydes providing the different enantiomers of the diarylmethanols with almost the same excellent enantioselectivities. The arylation method is also carried out in tandem with lactonization process to afford a concise synthetic approach to both enantiomers of optically active 3-aryl phthalide.

Enantioselective Friedel–Crafts Alkylation of Pyrrole with Chalcones Catalyzed by a Dinuclear Zinc Catalyst

A highly enantioselective Friedel-Crafts (F-C) alkylation of pyrrole with a wide range of simple nonchelating chalcone derivatives catalyzed by a chiral (Zn2EtL)n (L = (S,S)-1) complex has been developed. The catalyst (Zn2EtL)n complex was prepared in situ by reacting the chiral ligand (S,S)-1 with 2 equiv of diethylzinc. A series of β-pyrrole-substituted dihydrochalcones were usually formed mostly in excellent yields (up to 99%) and excellent enantioselectivity [up to 99% enantiomeric excess (ee)] by using 15 mol % catalyst loading under mild conditions. The absolute stereochemistry of the products was determined to be the S-configuration by X-ray crystallographic analysis of 13g. Meanwhile, a weak negative nonlinear effect was observed. On the basis of the experimental results and previous reports, a possible mechanism was proposed to explain the origin of the asymmetric induction.

Highly Enantioselective Catalytic System for Asymmetric Copolymerization of Carbon Dioxide and Cyclohexene Oxide

A new ligand can be easily prepared, and its intramolecular dinuclear zinc complexes act as a high performance catalyst for the asymmetric alternating copolymerization of cyclohexene oxide and CO2 under very mild conditions (1 atm CO2 , room temperature), affording completely alternating polycarbonates with up to 93.8 % enantiomeric excess (ee) and 98 % yield. A high Mn value of 28 600 and a relatively narrow polydispersity (Mw /Mn ratio) of 1.43 were also achieved.

A New Strategy for Enantioselective Construction of Multisubstituted Five-Membered Oxygen Heterocycles via a Domino Michael/Hemiketalization Reaction

A new highly enantioselective domino Michael/hemiketalization reaction of α-hydroxyacetophenone with β,γ-unsaturated α-keto esters for the synthesis of 2,2,4,5-tetrasubstituted chiral tetrahydrofurans is reported. With 2 mol % intramolecular dinuclear zinc-AzePhenol complex prepared in situ from the reaction of multidentate semi-azacrown ether ligand with ZnEt2 , the corresponding anti-multisubstituted tetrahydrofuran products were obtained in up to 90 % yields, and 98 % enantiomeric excess (ee) at 0 °C for 45 min. Moreover, the products were easily converted to 2,3,5-trisubstituted 2,3-dihydrofurans without any loss in optical activity.

Synthesis of dendrimer-supported ferrocenylmethyl aziridino alcohol ligands and their application in asymmetric catalysis

A series of N-ferrocenylmethyl aziridino alcohol ligands bearing Frechet-type dendrimers were synthesized and applied in the asymmetric addition of diethylzinc to aldehydes affording chiral alcohols in excellent yields (up to 99%) and excellent enantioselectivities (ee, up to 98%). The ligands could be recycled and reused eight times for such a reaction with almost the original high reactivity and selectivity.