Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Green Chemistry Center, Peking University, 202 Chengfu Road, 098#, Beijing 100871, China State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 200060, China

Transition-Metal-Free Coupling Reactions

As two coexisting and fast-growing research fields in modern synthetic chemistry, the merging of organocatalysis and C–H bond functionalization is well foreseeable, and the joint force along this line has been demonstrated to be a powerful approach in making inert C–H bond functionalization more viable, predictable, and selective. In this review, we provide a comprehensive summary of organocatalysis in inert C–H bond functionalization over the past two decades. The review is arranged by types of inert C–H bonds including alkane C–H, arene C–H, and vinyl C–H as well as those activated benzylic C–H, allylic C–H, and C–H bonds alpha to the heteroatom such as nitrogen and oxygen. In each section, the discussion is classified by the explicit organocatalytic mode involved.

Organocatalysis in Inert C–H Bond Functionalization

A metal-free, simple, and scalable method for the synthesis of the amides (III), (V), (VII), and (X) is developed from commercially available or easily synthesized starting materials.

Cross Coupling of Acyl and Aminyl Radicals: Direct Synthesis of Amides Catalyzed by Bu4NI with TBHP as an Oxidant

Recent achievements in the use of TBAI (tetrabutylammonium iodide) and TBHP (tert-butyl hydroperoxide) as an oxidation system have been summarized and discussed.

A powerful combination: recent achievements on using TBAI and TBHP as oxidation system

Metal‐Free Oxidative Carbon‐Heteroatom Bond Formation Through C–H Bond Functionalization

Title reaction proceeds in the absence of transition metal catalysts, is operationally simple and tolerates a wide variety of functional groups like cyano, amide, aromatic halide, ether, ketone groups and C—C double bonds.

Bu4NI‐Catalyzed C ? O Bond Formation by Using a Cross‐Dehydrogenative Coupling (CDC) Reaction

The invention belongs to the field of organic synthesis, in particular to a method for preparing a perester compound. The method comprises the following steps of: preparing reaction systems, mixing the reaction systems, reacting to prepare the perester compound under the condition of stirring. The reaction systems include reaction substrates, i.e., aldehyde and tert butyl hydrogen peroxide, a catalyst and solvents, wherein the catalyst is one of potassium iodide, sodium iodide, ammonium iodide, iodine, tetramethyl-ammonium iodide, tetraethyl-ammonium iodide, tetrapropyl-ammonium iodide, tetrabutyl-ammonium iodide, tetraethyl-ammonium iodide, 3-(trifluoromethyl) phenyl trimethyl ammonium iodide, ferrocene methyl trimethyl ammonium iodide, (propyl carbonyl sulfur-ethyl) trimethyl ammonium iodide, n, n-dimethyl methylene ammonium iodide or benzyl trimethyl ammonium iodide. The method provided by the invention has the advantages of wide applicable substrate range, mild reaction conditions, little consumption of strong alkali and environment friendliness.

Kai Xu

Papers

Bu4NI‐Catalyzed C ? O Bond Formation by Using a Cross‐Dehydrogenative Coupling (CDC) Reaction

Method for preparing perester compound

Bu4NI‐Catalyzed C—O Bond Formation by Using a Cross‐Dehydrogenative Coupling (CDC) Reaction.