351-36-0Relevant articles and documents
An Environmentally Benign, Catalyst-Free N?C Bond Cleavage/Formation of Primary, Secondary, and Tertiary Unactivated Amides
Kumar, Vishal,Dhawan, Sanjeev,Girase, Pankaj Sanjay,Singh, Parvesh,Karpoormath, Rajshekhar
, p. 5627 - 5639 (2021/11/11)
Herein, we report an operationally simple, cheap, and catalyst-free method for the transamidation of a diverse range of unactivated amides furnishing the desired products in excellent yields. This protocol is environmentally friendly and operates under extremely mild conditions without using any promoter or additives. Significantly, this strategy has been implied in the chemoselective synthesis of a pharmaceutical molecule, paracetamol, on a gram-scale with excellent yield. We anticipate that this universally applicable strategy will be of great interest in drug discovery, biochemistry, and organic synthesis.
Catalyst-free, direct electrochemical synthesis of annulated medium-sized lactams through C-C bond cleavage
Ackermann, Lutz,Huang, Zhixing,Kuniyil, Rositha,Li, Yueheng,Ruan, Zhixiong,Xu, Zhongnan,Zhang, Chao
supporting information, p. 1099 - 1104 (2020/03/11)
A catalyst-free, direct electrochemical synthesis of synthetically challenging medium-sized lactams through C-C bond cleavage has been developed. In contrast to previous typical amidyl radical cyclization, this electrosynthetic approach enabled step-economical ring expansion through a unique remote amidyl migration under mild, metal- and external-oxidant-free conditions in a simple undivided cell. The strategy features unparalleled broad substrate scope with all ring sizes of (hetero)aryl-fused 8-11-membered rings and hetero atom-tethered rings, high yields, and good functional group tolerance. Our experimental and computational findings provided strong support for a SET-based reaction manifold.
Selective C-F Functionalization of Unactivated Trifluoromethylarenes
Vogt, David B.,Seath, Ciaran P.,Wang, Hengbin,Jui, Nathan T.
supporting information, p. 13203 - 13211 (2019/09/03)
Fluorinated organic molecules are pervasive within the pharmaceutical and agrochemical industries due to the range of structural and physicochemical properties that fluorine imparts. Currently, the most abundant methods for the synthesis of the aryl-CF2 functionality have relied on the deoxyfluorination of ketones and aldehydes using expensive and poorly atom economical reagents. Here, we report a general method for the synthesis of aryl-CF2R and aryl-CF2H compounds through activation of the corresponding trifluoromethyl arene precursors. This strategy is enabled by an endergonic electron transfer event that provides access to arene radical anions that lie outside of the catalyst reduction potential. Fragmentation of these reactive intermediates delivers difluorobenzylic radicals that can be intercepted by abundant alkene feedstocks or a hydrogen atom to provide a diverse array of difluoalkylaromatics.
