Rhodium-catalyzed direct C-H amination of benzamides with aryl azides: a synthetic route to diarylamines.

Rhodium-catalyzed oxidative ortho-acylation of benzamides with aldehydes: direct functionalization of the sp2 C-H bond.

A rhodium-catalyzed oxidative acylation of benzamides with aryl aldehydes via direct sp(2) C-H bond cleavage is described. In the presence of [Cp*RhCl(2)](2), AgSbF(6), and silver carbonate as an oxidant, N,N-diethyl benzamides can be effectively carbonylated to yield ortho-acyl benzamides.

Synthesis of α,α-disubstituted aryl amines by rhodium-catalyzed amination of tertiary allylic trichloroacetimidates.

The rhodium-catalyzed regioselective amination of tertiary allylic trichloroacetimidates with unactivated aromatic amines is a direct and efficient approach to the preparation of α,α-disubstituted allylic aryl amines in good yield and with excellent regioselectivity. This method is applicable to a variety of unactivated primary and secondary amines and allows for the preparation of reverse pren...

Cobalt catalyzed sp3 C–H amination utilizing aryl azides† †Electronic supplementary information (ESI) available. CCDC 1057198–1057200. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc01162k

Nickel-catalyzed triarylamine synthesis: synthetic and mechanistic aspects.

An improved protocol was described for the amination of chloroarenes with diarylamines under NiCl2(PCy3)2 catalysis in the presence of a Grignard reagent as base. This method fully suits bromo-/iodoarene substrates as well, and even is expanded to certain aryl tosylates. A preliminary investigation into the mechanism suggests that this amination reaction might proceed through Ni(I) and Ni(III) ...

Copper-Catalyzed Ring-Expansion/Thiolactonization via Azidation of Internal Olefinic C–H Bond under Mild Conditions

A copper(I)-catalyzed, (diacetoxyiodo)benzene [PhI(OAc)2]-mediated ring-expansion/thiolactonization of a-oxo ketene dithioacetals was efficiently realized via azidation of the internal olefinic C@H bond with sodium azide under mild conditions. Sequential amination, ring-expansion rearrangement, and thiolactonization occurred to form aminated thiolactones in the presence of acetic anhydride as t...