Polyhalohydrocarbon Mediated Activation/Functionalization Of Aliphatic Tertiary Amines

The thesis aims at the studies on the copper-catalyzed activation/functionalization of aliphatic tertiary amines with the assistance of polyhalohydrocarbon. This dissertation includes two parts:Part1:Minireviews of activation/functionalization of the Csp3-H bond adjacent to nitrogen atomThe activation/functionalization of the Csp3-H bond adjacent to nitrogen atom were classified in four types:Csp3-Csp, Csp3-Csp2, Csp3-Csp3, Csp3-X. Some of the recently developed examples were described in chapter1. In addition, the reactions between CCl4and aliphatic amines were introduced in chapter2.Part2:Activation/functionalization of aliphatic tertiary amines mediated by polyhalohydrocarbon/CuXnFour novel activations/functionalizations of aliphatic tertiary amines mediated by polyhalohydrocarbon were successfully achieved. Lots of nucleophilic reagents were screened. Intensive studies were carried out to expand the range of applications of polyhalohydrocarbon/cat. copper. It includes:Sulfonyl amidines were synthesized by the reaction between tertiary amines and sulfonyl azides mediated by CuCl/CCl4-C2Cl6/CuI mediated alkynylation of aliphatic tertiary methylamine from terminal alkynes, and synthesis of methylene-bridged bis-1,3-dicarbonyl derivatives from1,3-dicarbonyl compounds. Mediated by CCl4/CuBr2, the oxidative coupling reactions between aniline derivatives and triethylamine to produce unsymmetrical urea derivatives were also investigated. A broad spectrum of substrates proved to be well tolerable. The protocols provided alternatively economical and convenient strategies for the efficient access to functionalization of aliphatic tertiary amines.