Photo-induced reductive cross-coupling of aldehydes, ketones and imines with electron-deficient arenes to construct aryl substituted alcohols and amines

Umpolung reactions of C=X bonds(X=O,N)are valuable ways of constructing new C–C bonds,which are sometimes difficult to be constructed using traditional synthetic pathways.Classical polarity inversion of C=X bonds(X=O,N)usually requires air or moisture‐sensitive and strong reducing agents,which limit the feasibility of substrate scope.Herein we describe a photo‐induced reductive cross‐coupling reaction of aldehydes,ketones and imines with electron‐deficient arenes(aromatic nitriles)using fac‐Ir(ppy)3as a photocatalyst and diisopropylethylamine(DIPEA)as a terminal reductant under visible light irradiation.Mild conditions and high yields mean that this new polarity inversion strategy can be used with aryl‐substituted alcohols and amines.Spectroscopic studies and control experiments have demonstrated the oxidative quenching of Ir(ppy)3*by electron‐deficient arenes involved in the key step for the C–C bond formation.

Direct N-alkylation of amines with alcohols using AlCl_3 as a Lewis acid

A substitution reaction of amines with alcohols for N-alkylated amines has been developed using inexpensive AlCl3without any ligand or additive.Either aromatic or aliphatic amines and primary or secondary alcohols perform the AlCl3-mediated reaction smoothly to afford various N-alkylated amines in satisfactory yields.

Preparation of aromatic nitriles via direct oxidative conversion of benzyl alcohols,aldehydes and amines with pentylpyridinium tribromide in aqueous NH_4OAc

Pentylpyridinium tribromide and aqueous ammonium acetate was used for the rapid oxidative conversion of benzyl alcohols, benzaldehydes and benzyl amines to the corresponding benzonitriles in good to excellent yields. This simple, mild and one-pot system provides easy workup and separation of the products.

Magnetic wrinkled organosilica-based metal-enzyme integrated catalysts for enhanced chemoenzymatic catalysis

Core-shell structured magnetic wrinkled organosilica-based metal-enzyme integrated catalysts were synthesized,and their catalytic performances were studied in the chemoenzymatic dynamic kinetic resolution of chiral amines in an organic solvent,as well as in the chemoenzymatic synthesis of chiral alcohols in water.Structureperformance studies revealed the important influence of their tunable structure and composition on the optimization of activity,stability,and recyclability in chemoenzymatic catalysis.