Enantioselective Reaction of 2H‐Azirines with Phosphite Using Chiral Bis(imidazoline)/Zinc(II) Catalysts

The first highly enantioselective nucleophilic addition reaction of phosphites with 2H ‐azirines has been developed. The reaction was applied to various 3‐substituted 2H ‐azirines using novel chiral bis(imidazoline)/Zn^II catalysts to afford products in good yield with high enantioselectivity. The transformation of the obtained optically active aziridines showed that 2H ‐azirines act as either α,β‐ or β,β‐dicarbocationic amine synthons.     

Catalytic Enantioselective Reaction of α‐Phenylthioacetonitriles with Imines Using Chiral Bis(imidazoline)–Palladium Catalysts

The catalytic enantioselective reaction of α‐phenylthioacetonitriles with imines has been developed. The reaction of various imines proceeds in good yields and diastereo‐ and enantioselectivities in the presence of chiral bis(imidazoline)–palladium catalysts. The obtained products can be converted into β‐aminonitrile or β‐aminoamide compounds without loss of enantiopurity.     

Catalytic Enantioselective Reaction of α‐Aminoacetonitriles Using Chiral Bis(imidazoline) Palladium Catalysts

The catalytic enantioselective reaction of diphenylmethylidene‐protected α‐aminoacetonitriles with imines has been developed. Good yields and diastereo‐ and enantioselectivities were observed for the reaction of various imines using chiral bis(imidazoline)/Pd catalysts. The reaction of α‐aminonitriles with di‐tert‐butyl azodicarboxylate afforded chiral α,α‐diaminonitriles in high yields with high enantioselectivities.     

Enantioselective Reaction of 2H-Azirines with Phosphite Using Chiral Bis(imidazoline)/Zinc(II) Catalysts

The first highly enantioselective nucleophilic addition reaction of phosphites with 2H-azirines has been developed. The reaction was applied to various 3-substituted 2H-azirines using novel chiral bis(imidazoline)/Zn^II catalysts to afford products in good yield with high enantioselectivity. The transformation of the obtained optically active aziridines showed that 2H-azirines act as either α,β- or β,β-dicarbocationic amine synthons.     

Catalytic Enantioselective Methylene C(sp3)−H Amidation of 8‐Alkylquinolines Using a Cp*RhIII/Chiral Carboxylic Acid System

Catalytic enantioselective directed methylene C(sp³)?H amidation reactions of 8‐alkylquinolines using a Cp*Rh^III/chiral carboxylic acid (CCA) hybrid catalytic system are described. A binaphthyl‐based chiral carboxylic acid efficiently differentiates between the enantiotopic methylene C?H bonds, which leads to the formation of C?N bonds with good enantioselectivity.     

Catalytic Enantioselective Synthesis of 2,5‐Dihydrooxepines

A Michael addition initiated cyclopropanation/retro‐Claisen rearrangement tandem reaction was developed for the enantioselective synthesis of highly functionalized 2,5‐dihydrooxepines. In the presence of a chiral oxazaborolidinium ion (COBI) catalyst, the reaction proceeds to give good yields and high enantioselectivity.     

Catalytic Enantioselective Protonation/Nucleophilic Addition of Diazoesters with Chiral Oxazaborolidinium Ion Activated Carboxylic Acids

A new chiral Brønsted acid derived from carboxylic acid and a chiral oxazaborolidinium ion (COBI), as an activator, is introduced. This acid was successfully applied as a catalyst for the highly enantioselective protonation/nucleophilic addition of diazoesters with carboxylic acids.     

Enantioselective Addition Reaction of Azlactones with Styrene Derivatives Catalyzed by Strong Chiral Brønsted Acids

An enantioselective intermolecular addition reaction of azlactones, as carbon nucleophiles, with styrene derivatives, as simple olefins, was demonstrated using a newly developed chiral Brønsted acid catalyst, namely, F₁₀BINOL‐derived N‐triflyl phosphoramide. Addition products having vicinal tetrasubstituted carbon centers, one of which is an all‐carbon quaternary stereogenic center, were formed in good yields with moderate to high stereoselectivities. Extremely high acidity of the new chiral Brønsted acid was confirmed by its calculated pK_a value based on DFT studies and is the key to accomplishing not only high catalytic activity but also efficient stereocontrol in the intermolecular addition.     

Chiral Cyclopentadienyl Iridium(III) Complexes Promote Enantioselective Cycloisomerizations Giving Fused Cyclopropanes

The cyclopentadienyl (Cp) group is a very important ligand for many transition‐metal complexes which have been applied in catalysis. The availability of chiral cyclopentadienyl ligands (Cp^x) lags behind other ligand classes, thus hampering the investigation of enantioselective processes. We report a library of chiral Cp^xIr^III complexes equipped with an atropchiral Cp scaffold. A robust complexation procedure reliably provides Cp^xIr^III complexes with tunable counterions. In a proof‐of‐concept application, the iodide‐bearing members are shown to be highly selective for enyne cycloisomerization reactions. The dehydropiperidine‐fused cyclopropane products are formed in good yields and enantioselectivities.     

Catalytic Biomimetic Asymmetric Reduction of Alkenes and Imines Enabled by Chiral and Regenerable NAD(P)H Models

The development of biomimetic chemistry based on the NAD(P)H with hydrogen gas as terminal reductant is a long‐standing challenge. Through rational design of the chiral and regenerable NAD(P)H analogues based on planar‐chiral ferrocene, a biomimetic asymmetric reduction has been realized using bench‐stable Lewis acids as transfer catalysts. A broad set of alkenes and imines could be reduced with up to 98 % yield and 98 % ee, likely enabled by enzyme‐like cooperative bifunctional activation. This reaction represents the first general biomimetic asymmetric reduction (BMAR) process enabled by chiral and regenerable NAD(P)H analogues. This concept demonstrates catalytic utility of a chiral coenzyme NAD(P)H in asymmetric catalysis.