Transformations Of Unsaturated Hydrocarbons Through C-H Oxidative Radical Functionalization Reactions

The carbon-hydrogen bond is one of the most common bonds that found in the organic compounds. It is a constituent element of the majority of organic molecules with the features of a short bond length and a high bond energy. Consequently, C-H functionalization has been one of the most important research directions in organic chemistry. However, the development of a general approach for the site-selective functionalization of ubiquitous C-H bonds, especially the unactivated C-H bonds, still remains a great challenge due to the low reactivity and hard selectivity control.The C-H oxidative radical functionalization reaction provides an efficient alternative to functionalization of the C-H bond under mild conditions. The process involves the generation of a free radical from the cleavage of the C-H bond in the present of an oxidant followed by the introduction of the functional group. The C-H oxidative radical functionalization reaction is highly efficient, easy to operate, low toxicity and environmentally-benign, highly atom economic. Thus, the C-H oxidative radical functionalization reaction has recieved more and more attention to form diverse chemical bonds in organic synthesis with tremendous applications in both academia and industry.This dissertation mainly focuses on transformations of unsaturated hydrocarbons through the C-H oxidative radical functionalization reaction, and the contents of this dissertation involves six parts.(1) Recent advances in the C-H oxidative carbon radical coupling reaction are summarized in detail. Four different reactions involved in the reaction are discussed in this chapter:(i) the C-H oxidative carbon radical coupling initiated the reactions with alkenes;(ii) the C-H oxidative carbon radical coupling initiated the reactions with alkynes;(iii) the C-H oxidative carbon radical coupling initiated the reactions with 1, n-enynes; and(iv) the C-H oxidative carbon radical coupling initiated the reactions with heteroatom functional groups.(2) A new strategy for the Fe-catalyzed oxidative 1,2-alkylarylation of alkenes is presented in the second chapter. This method allows the synthesis of a variety of functionalized oxindoles through difunctionalization of the alkenes under the Fe Cl3/t-Bu OOH catalytic oxidation system. This transformation proceeds efficiently under mild and simple conditions and is compatible with a variety of functional groups.(3) A copper-catalyzed oxidative ipso-carboalkylation of alkynes was illustrated in the third chapter. Under a catalytic amount of copper, an ether is efficiently introduced to produce the spirocyclic compounds by ipso-cyclization of alkynes. This transformation involves the formation of two new C-C bonds and one C=O bond.(4) A copper-catalyzed oxidative α-alkylation of α-amino carbonyl compounds is described in the fourth chapter. Under the efficient Cu Cl2/t-Bu OOH catalytic oxidation system, complex α-etherified α-amino carbonyl derivatives were synthesized from the corresponding simple α-amino carbonyl compounds and ethers. This method achieves two C(sp3)-H bond activation through the formation of a new C-C bond.(5) A copper-catalyzed oxidative oxyalkylation of enol ethers is showed in the fifth chapter. A series of amino acid derivatives are synthesised through the difunctionalization of target enol ethers. The method uses readily available-amino carbonyl compounds as the alkyl resources and simple hydroperoxides as the alkoxy resources. This transformation proceeds good selectivity and tolerates a range of functional groups. In this process, hydroperoxides not only use as terminal oxidants, but also play a role of reagent, which greatly enriched their function in organic chemistry.(6) A oxidative coupling of alkenes with aldehydes and hydroperoxides is descirbed in the last chapter. This method provides the access to the important 2,3-epoxy ketones via base-promoted difunctionalization of alkenes through oxidative radical reaction in one pot under mild conditions. This transformation involves the formation of two C-O bonds and one C-C bond.