71982-24-6Relevant articles and documents
Catalytic Amination of Phenols with Amines
Chen, Kai,Kang, Qi-Kai,Li, Yuntong,Wu, Wen-Qiang,Zhu, Hui,Shi, Hang
supporting information, p. 1144 - 1151 (2022/02/05)
Given the wide prevalence and ready availability of both phenols and amines, aniline synthesis through direct coupling between these starting materials would be extremely attractive. Herein, we describe a rhodium-catalyzed amination of phenols, which provides concise access to diverse anilines, with water as the sole byproduct. The arenophilic rhodium catalyst facilitates the inherently difficult keto–enol tautomerization of phenols by means of π-coordination, allowing for the subsequent dehydrative condensation with amines. We demonstrate the generality of this redox-neutral catalysis by carrying out reactions of a large array of phenols with various electronic properties and a wide variety of primary and secondary amines. Several examples of late-stage functionalization of structurally complex bioactive molecules, including pharmaceuticals, further illustrate the potential broad utility of the method.
Metal-free late-stage C(sp2)-H functionalization of: N -aryl amines with various sodium salts
Mudithanapelli, Chandrashekar,Kim, Mi-Hyun
, p. 450 - 464 (2020/02/03)
Metal-free consecutive C(sp2)-X (X = Cl, Br, S, N) bond formations of N-aryl amines (cyclic, fused, carbamate, and aminium radicals) were achieved under mild conditions using [bis(trifluoroacetoxy)iodo]benzene (PIFA) and simple nonharmful sodium salts. This direct and selective C(sp2)-H functionalization showed excellent functional group compatibility, cost effectiveness, and late-stage applicability for the synthesis of biologically active natural products. Two mechanisms were proposed to explain the ortho- or para-preference, as well as the accelerating effect of CH3NO2
PIFA-Promoted, Solvent-Controlled Selective Functionalization of C(sp2)-H or C(sp3)-H: Nitration via C-N Bond Cleavage of CH3NO2, Cyanation, or Oxygenation in Water
Mudithanapelli, Chandrashekar,Dhorma, Lama Prema,Kim, Mi-Hyun
supporting information, (2019/05/07)
A novel nitration (via C(sp3)-N breaking/C(sp2)-N formation with CH3NO2) mediated by [bis(trifluoroacetoxy)iodo]benzene (PIFA) is described. The NO2 transfer from CH3NO2 to the aromatic group of the substrate is possible with careful selection of the solvent, NaX, and oxidant. In addition, the solvent-controlled C(sp2)-H functionalization can shift to an α-C(sp3)-H functionalization (cyanation or oxygenation) of the α-C(sp3)-H of cyclic amines.