Zn（OTF）₂-Catalyzed Hydroamination Of Ynamides With Aromatic Amines

Nitrogen-containing compounds are widely present in natural products,drug molecules and various chemical products,and they play an indispensable role in people’s lives.For example,natural alkaloid compounds isolated from medicinal plants are the most representative type of nitrogen-containing compounds.They not only show great application potential in the treatment of diseases,but also guide the synthesis of nitrogen-containing drugs.Among the 200best-selling drugs in 2019,more than 90 are nitrogen-containing heterocyclic compounds.The related research of nitrogen has become a hot spot in the field of organic synthesis,and the establishment of efficient C-N bond is one of the key issues.As an N-substituted alkyne compound,ynamides are general motif for the synthesis of nitrogen-containing compounds,and its application value is worth further exploring in the method of constructing C-N bonds.This thesis explored the optimal conditions for the hydroamination of ynamides and aromatic primary amines based on cheap Lewis acid catalysis,and established a new methodology for the synthesis of a series of compounds containing amidine groups.The main results of this paper are as follows:1.By known synthetic methods,12 ynamides with different substituents were prepared.2.The hydroamination reaction of ynamides 2-51a~2-51 l and aniline compounds 3-7a~3-7u catalyzed by Zn(OTf)2 was optimized,and a new method for the synthesis of amidine compounds 3-9aa~3-9ua、3-9ab~3-9ik and 3-9pa~3-9rk was established.Verified by 37 substrates,this method has a relatively high yield 50%~93% and good regioselectivity.3.By known methods,the amidine compound 3-9aa was transformed,and the indole compound 2-52 was synthesized with a yield of 65%.