The Synthesis And Application Of Methylene Bridged Compound Based On CDC Reaction

Cross dehydrogenation coupling(CDC) is a reaction using the C-H bonds of the reagents to form C-C bonds directly under oxidative condition. This reaction without using reagent with active functional groups, save a lot of preparation process of pre-functionalized materials, thus realized the shorter synthetic route and higher atom efficiency. Cross dehydrogenation coupling reaction provides an important method in order to form C-C bonds, is an important research content in the field of modern organic synthesis. And widely used in the medical synthesis, materials science and other fields. Our group synthesized methylene-bridged compounds and dihydrofuran efficiently based on the CDC reaction.In the system of Cu I/air can synthesize methylene-bridged compounds efficiently. Under the condition of CuI as catalyst, air as oxidant, N, N, N, Ntetramethylethylenediamine(TMEDA) and acyl acetate green highly effective, and selective synthesis of methyl-bridged compounds based on CDC reaction. And the applicability of this system is good, for the majority of similar compounds can achieve the desired production rate.I2 catalyzed the synthesis of methylene-bridged compounds. Under the condition of non-metallic I2 as catalyst in this reaction, tert-butyl ether peroxide as oxidant, N, N, N, N- tetramethylethylenediamine(TMEDA) and acyl acetate also can synthesize series of methylene-bridged compounds efficiently. This reaction avoid using transition metal, so it has advantages in the synthesis of pharmaceuticals.CuCl2 promote or catalyzed the synthesis of dihydrogen furan ring compounds. The reaction in CuCl2 promote and tert-butyl ether peroxide as oxidant, N, N, N, Ntetramethylethylenediamine(TMEDA) and acyl acetate synthesized dihydrogen furan compounds efficiently and high selectivily. And the applicability of this system is good, for the majority of substrate can achieve the desired production rate. In addition, the reaction under the condition of catalytic amount of CuCl2 and 1.2 eq NBS is added in the system can also undertake, and other similar compounds can be moderate to high yield rate.I2 catalyzed the synthesis of 3-aldehyde indole.Using non-metallic I2 as catalyst, O2 as oxidant, N, N, N, N- tetramethylethylenediamine(TMEDA) and indole synthesized a series of 3-aldehyde indole compounds green and efficiently. Production rate can be reached moderate to high yield rate. Through our research, we found that the N-substituted indoles performanced poor activity than unsubstituted indoles.