氨基二烯类化合物对映选择性去对称化氢胺化反应的研究

RESEARCH ON ENANTIOSELECTIVE DESYMMETRIZATION OF AMINODIALKENES THROUGH HYDROAMINATION OF ALKENES

鱼章龙

11649068

硕士

化学

刘心元

2018

2018.7.11

哈尔滨工业大学

深圳

有机含氮化合物广泛地存在于自然界中，因其广泛易得，可以通过各种已知化学反应转换成重要的化工中间体，因而在农药、化妆品、医药用品的合成中有着极其广泛的应用。氢胺化反应是合成有机含氮化合物的重要方法，利用去对称化策略实现高对映选择性和非对映选择性的氢胺化反应无论是在药物的合成中，还是在天然产物的全合成中都有着重要的作用。本论文着眼于构建一种简洁高效地构建手性吡咯烷类化合物的方法。论文第一章简要介绍了该领域的研究背景与重要性及研究进展，分析了尚待解决的具体问题。之后通过底物的设计，催化剂的选择以及反应条件的筛选与优化，得到了最佳的反应条件。本文以氨基上带有硫脲基团保护的氨基二烯类化合物为反应底物，在手性布朗斯特酸的催化下，发生分子内的去对称化反应，在一步反应中高非对映、对映选择性地生成了有两个手性季碳中心的吡咯烷类化合物。

Organic nitrogen-containing compounds are widely found in nature. They have extremely wide applications in the synthesis of pesticides, cosmetics, and medical supplies because they are widely available and can be converted into important chemical intermediates through various chemical reactions. Hydroamination is an important method for the synthesis of organic nitrogen-containing compounds and The use of desymmetrization strategy to achieve high enantioselective and diastereoselective hydroamination reactions plays an important role both in the synthesis of medicine and the synthesis of natural products. This thesis focuses on developing a simple and efficient method for the construction of chiral pyrrolidines.In the first chapter we briefly introduce the research background and importance and the research progress in this field, and analyze the specific issues that need to be solved.Then through designing the substrate, screening the reaction parameters, we obtained the optimal reaction conditions for the enantioselective desymmetric hydroamination reaction.The chiral Brønsted acid-catalyzed intramolecular enantioselective desymmetric hydroamination of aminodialkenes has been successfully developed, providing access to a variety of diversely functionalized chiral pyrrolidines bearing two stereocenters, even including two remote quaternary stereocenters, with excellent efficiency as well as enantio- and diastereoselectivity under mild and user-friendly synthetic conditions.

有机催化 布朗斯特酸 去对称化 氢胺化 吡咯烷

Organic Catalysis Brønsted Acid Desymmetrization Hydroamination Pyrrolidines

中文

联合培养

南方科技大学

鱼章龙. 氨基二烯类化合物对映选择性去对称化氢胺化反应的研究[D]. 深圳. 哈尔滨工业大学,2018.