Professor Tian Shikai's research team of China University of science and technology: Stevens rearrangement of α - amino acid derived third-order allyl, propargyl and benzylamine with epoxide participation

The third-order allylic, propargylic and benzyl amines derived from lead α - amino acids are relatively stable, but they can rearrange after forming quaternary ammonium salt In recent years, transition metals such as PD and carbene have been used to catalyze the rearrangement of ammonium ylide However, they usually need special substrates and precious transition metals In 2016, Professor Tian Shikai's research team of University of science and technology of China first realized the Stevens rearrangement of allylamine using phenylyne (org Lett 2016, 18, 4872) The use of phenylalkyne can avoid the use of precious metals and realize the rearrangement of various tertiary amines Inspired by the previous work, recently, the research group has developed a method of Stevens rearrangement of allyl, propargyl and benzylamine with epoxy compounds Relevant research results were published in Chem EUR J (DOI: 10.1002 / chem 201900635) Introduction to Professor Tian Shikai, Professor, doctoral supervisor He graduated from chemistry department of Lanzhou University in 1993 with a Bachelor of Science degree In 1996 and 1998, he received his master of Science degree and doctor of Science degree from Shanghai Institute of organic chemistry, Chinese Academy of Sciences From 1999 to 2002, he worked as a postdoctoral researcher in the Department of chemistry, Brandeis University, USA 2002-2005 researcher in vertex pharmaceutical company, USA Since 2005, he has been a professor in the Department of chemistry, University of science and technology of China The main research direction is organic synthesis Leading scientific research achievements: Stevens rearrangement of α - amino acid derived third-order allyl, propargyl and benzylamine involved in epoxide Firstly, the author explored the reaction conditions with allylamine 1a and epoxy compound 2a, and found that no product was obtained without catalyst (Table 1) When organic acids and Lewis acids such as aluminum chloride and bismuth chloride are used, the reaction can not take place When FeCl 3 is used as catalyst, the product can be obtained with 60% separation yield Then, the common Lewis acid catalysts and solvents were screened It was found that when ZnI2 was used as catalyst and 1,4-dioxane was used as solvent, the product could be obtained with 89% separation yield Surprisingly, when amide is used as raw material, the reaction can also get medium separation yield (source: chem EUR J.) then, the author developed the substrate The allylamine reaction with different functional groups on alkenes can achieve medium yield It should be noted that allyl rearrangement occurs preferentially when benzyl and propargyl groups are attached to nitrogen atoms When using epoxy compounds with different substituents, the target product (scheme 2) can also be obtained in medium yield When propargylic tertiary amines are used, Stevens rearrangement can take place to obtain the dienes (scheme 3) When benzyl tertiary amines are used, 1,2-stevens rearrangement can take place to obtain benzylamines (scheme 4) These products have the basic framework of a large number of drug molecules and bioactive molecules, and have potential application value (source: chem EUR J.) (source: chem EUR J.) (source: chem EUR J.) finally, the author derived the naturally existing amino acids (scheme 4) The results show that the complex ternary bicycles can be obtained by using the standard conditions, and the chiral transfer effect is good (source: chem EUR J.) Professor Tian Shikai's research team has developed a Stevens rearrangement reaction involving epoxides of allyl, propargyl and benzylamine, which provides a simple and efficient method for the synthesis of multi substituted morpholine-2-one compounds This method not only has a wide range of substrate applications and better chiral transfer effect, but also provides a new idea and strategy for the realization of C-N bond breaking This article was recently published in Chem EUR J (DOI: 10.1002 / chem 201900635) Jin Youxiang, a doctoral student at the University of science and technology of China, and Yu Bangkui, the co-author of this paper are Professor Tian Shikai Nowadays, people and scientific research have been paid more and more attention in the economic life China has ushered in the "node of science and technology explosion" Behind the progress of science and technology is the work of countless scientists In the field of chemistry, in the context of the pursuit of innovation driven, international cooperation has been strengthened, the influence of Returned Scholars in the field of R & D has become increasingly prominent, and many excellent research groups have emerged in China For this reason, CBG information adopts the 1 + X reporting mechanism CBG information, chembeangoapp, chembeango official microblog, CBG wechat subscription number and other platforms jointly launch the column of "people and scientific research", approach the domestic representative research group, pay attention to their research, listen to their stories, record their demeanor, and explore their scientific research spirit.