Studies On Alkynylation Of Unactivated C(sp~3)-H Bond And Triphenylmethylation Of Acrylic Acid Decarboxylation

In this paper, metal-free alkynylation of unactivated C(sp~3)-H bond and copper-promoted decarboxylative trifluoromethylthiolation of ?,?-unsaturated carboxylic acid were introduced. The work of this paper is divided into the following two parts:Chapter one inroduces the alkynylation of unactivated C(sp~3)-H bond. Alkynyl compounds are very important structural groups in materials chemistry, biochemistry and medicine. Traditional approaches for the formation of C(sp~3)-C(sp) bonds involve nucleophilic attack of alkane halides with alkane reagents. Most methods use metal catalysts, which are expensive and environmentally hazardous. Therefore, the development of mild, green C(sp~3)-C(sp) bonds construction method has potential practical significance.In this paper, ethynylbenziodoxolones and unactivated alkanes as the object of study.The reaction conditions were explored, mainly to study the type and amount of oxidants, the reaction temperature on the reaction. Finally determine the use of 1 equiv DTBP, 1 mL alkanes as solvent, and reacted at 100 ? for 16 h. Different kinds of unactivated alkanes and ethynylbenziodoxolones were obtained by one-pot reaction.We also discussed the possible mechanism.The second part describes the copper-mediated decarboxylative trifluoromethylthiolation of ?,?-unsaturated carboxylic acid, trifluoromethylthio compounds have been widely utilized in the fields of pharmaceuticals, agrochemicals and functional materials due to the SCF3 group(s) can alter their polarity, lipophilicity and metabolic stability. Hence, it has been of great synthetic interest to develop new methods for the incorporation of SCF3 group(s) into organic molecules.An efficient method for the CuSO4·5H2O promoted trifluoromethylthiolation via the trifluoromethylthio radical attack of ?,?-unsaturated carboxylic acid copper salt t by using AgSCF3 has been developed. The method employs readily available chemicals,the reaction is experimentally simple and exhibiting wide functional group tolerance. In addition, experimental results indicated that the SCF3 radical is involved in the transformation by use of a radical scavenger 2,2,6,6-tetramethyl-l-piperdinyloxy(TEMPO).