Asymmetric Synthesis of α-Alkylated γ-Lactam via Nickel/8-Quinim-Catalyzed Reductive Alkyl-Carbamoylation of Unactivated Alkene

Chiral-auxiliary-mediated synthesis represents the most frequently used synthetic tool for the induction of chirality on α-position of γ-lactams in organic synthesis. However, the general strategy requires the stoichiometric use of chiral reagents with multiple manipulation steps. Transition-metal-catalyzed asymmetric alkene dicarbofunctionalization using readily available substrates under mild conditions allows the simultaneous construction of two vicinal chemical bonds and a chiral carbon center, hence, gain expedient access to chiral heterocycles. Herein, we disclose a Ni-catalyzed enantioselective reaction of 3-butenyl carbamoyl chloride and primary alkyl iodide enabled by a newly designed chiral 8-quinoline imidazoline ligand (8-Quinim). This protocol features broad functional group tolerance and high enantioselectivities, achieving unprecedented synthesis of chiral nonaromatic heterocycles via catalytic reductive protocol.1 Introduction2 Development of 8-Quinim Ligand3 Nickel/8-Quinim-Catalyzed Enantioselective Synthesis of Chiral α-Alkylated γ-Lactam4 Conclusion and Outlook

Chiral spiro phosphoric acid-catalysed enantioselective reaction of ketenes with N–H pyrroles

A chiral spiro phosphoric acid-catalyzed enantioselective reaction of ketenes with N–H pyrroles leads to enantioenriched C-acylated pyrroles bearing α-stereogenic carbon centres.

Organocatalytic regio-, diastereo- and enantioselective γ-additions of isoxazol-5(4H)-ones to β,γ-alkynyl-α-imino esters for the synthesis of axially chiral tetrasubstituted α-amino allenoates

The chiral phosphoric acid catalyzed regio-, diastereo- and enantioselective reaction of isoxazol-5(4H)-ones with β,γ-alkynyl-α-imino esters has been developed.

Enantioselective Construction of Tetrasubstituted Center of Chirality in Isoindolinones via Organocatalyzed Reaction Between Ketones and N-Acyl Ketimines

An efficient enantioselective reaction between ketones and N-acyl ketimines is described. In a reaction catalyzed by a chiral phosphoric acid, a broad range of ketones and ketimines afforded isoindolinone derivatives...

The Use of Ion Liquids as a Trojan Horse Strategy in Enzyme-Catalyzed Biotransformation of (R,S)-Atenolol

The enzymatic method was used for the direct biotransformation of racemic atenolol. The catalytic activities of commercially available lipases from Candida rugosa were tested for the kinetic resolution of (R,S)-atenolol by enantioselective acetylation in various two-phase reaction media containing ionic liquids. The composed catalytic system gave the possibility to easy separate substrates and products of the conducted enantioselective reaction and after specific procedure to reuse utilized enzymes in another catalytic cycle.

Amine-Catalyzed Decarboxylative Aldol Reaction of β-Ketocarboxylic Acids with Trifluoropyruvates

Decarboxylative aldol reaction of aliphatic carboxylic acids is a useful method for C–C bond formation because carboxylic acids are an easily available class of compounds. In this study, we found that the decarboxylative aldol reaction of tertiary β-ketocarboxylic acids and trifluoropyruvates proceeded smoothly to yield the corresponding aldol products in high yields and with high diastereoselectivity in the presence of a tertiary amine catalyst. In this reaction, we efficiently constructed a quaternary carbon center and an adjacent trifluoromethylated carbon center. This protocol was also extended to an enantioselective reaction with a chiral amine catalyst, and the desired product was obtained with up to 73% enantioselectivity.