Copper Or Silver-catalyzed Oxidative Radical Transformations Of Alkanes And Unsaturated Hydrocarbons

Unsaturated hydrocarbons(alkenes or alkynes)are hydrocarbon compounds contianing carbon-carbon double bonds or carbon-carbon triple bonds.The unsaturated bonds represent as a class of common functional groups that widely existed in massive of organic molecules including drugs,natural products and fine chemicals.Unsaturated hydrocarbons are versatile building blocks and widely used for the electrophilic reactions,nucleophilic reactions and free radical addition reactions,which play an indispensable role in organic synthesis,drug synthesis and oregano functional synthesis.In addition,alkanes are a kind of important large petrochemical products,and their efficient and high-valued transformations still remain a great challenging area.Transformations of alkanes and unsaturated hydrocarbons are a ongoing hot-topic and chanlleging.In recent years,impressive advances in transformations of alkanes and unsaturated hydrocarbons via C-H functionalization have been achieved.In contrast to the classical cross-coupling reactions,transformations of alkanes and unsaturated hydrocarbons relying on the C-H functionalization avoid the use of organohalides.However,transition-metal catalyzed C-H bond activation reactions are limited to the pre-functionalized direct group and complex metal catalysts.Therefore,development of new C-H functionalization strategies for transformations of alkanes and unsaturated hydrocarbons is highly desirable and important.Owing to simple catalytic systems and broad substrate scope of the oxidative radical strategy,it might provide a powerful method to transform the alkanes and unsaturated hydrocarbons.This dissertation focuses on the transformations of alkanes and unsaturated hydrocarbons and the synthesis of new unsaturated hydrocarbons by the oxidative radical strategy,especially C-H oxidative radical strategy.The contents of this dissertation include copper or silver-catalyzed oxidative radical transformations of alkanes and unsaturated hydrocarbons.This dissertation consists of five parts as following:In the first chapter,recent process in the oxidative radical strategy for the transformations of alkanes and unsaturated hydrocarbons are summarized.From the perspective of the catalytic system,substrates and mechanisms,four types of reactions were reviewed in detail,including the oxidative radical difunctionalization of alenes,the oxidative radical coupling of alenes,the oxidative radical difunctionalization of alkynes and the oxidative radical coupling of alenes/alkynes.In the second chapter,a new copper-catalyzed oxidative radical reaction for the synthesis of functionalized intermediate olefins is described.The common alkanes couple with acids and selectively afford allylic esters and alkylalkenes under this oxidative system using DTBP as oxidant and a catalytic amount of K2CO3 as promoter.This method achieves multiple dehydrogenation and esterification,representing a new unactivated C(spP)-H oxidative esterification of acids with common alkanes.In the third chapter of this dissertation,a new copper-facilitated oxidative cyclization of 2-allenyl-1,1'-biphenyls with a-carbonyl alkyl bromides for producing functionalized phenanthrenes is presented.The allenes possess different reaction properties from common olefins due to its structure containing two cumulative carbon-carbon double bonds.This radical reaction represents the first allene 2,3-dicarbofunctionalization triggered by oxidative radical-medicated C3-addition of the terminal allene moiety and C-Br/C-H functionalization.In the fourth chapter,a new silver-promoted oxidative ring-opening/alkynylation of cyclopropanols with ethynyl benziodoxolones(EBXs)is described.This method enables the formation of alkyl alkynes via a sequence of ring-opening and alkynylation.The control experiments support a radical mechanism for the silver-promoted method.This oxidative radical reaction provides an efficient method for the introduction of an alkynyi group on an unactivated C(sp3)of a molecule.