A simple and efficient method for transition-metal-free N-arylation of various amines by triarylsulfonium triflates is described. Both aliphatic and aromatic amines were smoothly converted at 80 °C in the presence of tBuOK or KOH to give the corresponding mono N-arylated products in good to high yields. The molar ratios of the reactants and the choice of bases had a big effect on the reaction. When a large excess of [Ph3 S][OTf] and tBuOK were employed for primary amines under the standard conditions, the bis(N-phenyl) products were predominantly formed. This method was also applicable to the synthesis of bioactive N-phenyl amino acid derivatives. The control experiments, the deuterium labelling study, and the presence of regioisomers of N-arylated products when using 4-substituted triarylsulfonium triflates suggested that the reaction might proceed through an aryne intermediate. The present protocol demonstrated that triarylsulfonium salts are versatile arylation reagents in the construction of CAr -N bonds.

Transition-Metal-Free N-Arylation of Amines by Triarylsulfonium Triflates.

Efficient N-arylation of azole compounds utilizing selective aryl-transfer TMP-iodonium(III) reagents

Arylations Promoted by Hypervalent Iodine Reagents

Cu-catalyzed N-3-Arylation of Hydantoins Using Diaryliodonium Salts

A series of quaternary ammonium-based (QAB) functionalized polyacrylonitrile fibers as superbase catalysts for C—C bond forming reactions in water were prepared. Alkyl with different chain lengths ...

Quaternary Ammonium-Based Functionalized Polyacrylonitrile Fibers with Polarity Tunable Inner Surface Microenvironment for C–C Bond Forming Reactions under Continuous Flow Conditions

A novel synthetic methodology was developed for the N-arylation of nitroenamine derivatives utilizing diaryliodonium triflates and copper(I) chloride as a catalyst. The procedure enables the easy aryl transfer from the hypervalent species under mild catalytic conditions with unusual heteroatom preference and high efficiency.

Copper-Catalyzed N-Arylation of Nitroenamines with Diaryliodonium Salts

Simple route to new oxadiazaboroles and oxadiazoles via amidoximes

1-Cyanomethylene-6,7-dimethoxy-1,2,3,4-tetrahydro-isoquinoline reacts with α,β-unsaturated aldehydes and ketones in presence of cerium(III) chloride, to yield benzo[a]quinolizines. α-Alkyl substituted unsaturated aldehydes under the same conditions, however, afford pyrrolo[2,1-a]isoquinolines.

Zoltán Vincze

Papers

Copper-Catalyzed N-Arylation of Nitroenamines with Diaryliodonium Salts

Simple route to new oxadiazaboroles and oxadiazoles via amidoximes

Cerium(III)-catalyzed cyclizations with 1-cyanomethylene tetrahydroisoquinoline: Substituent controlled formation of fused pyrroles or pyridines