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对铑催化的1,6-烯炔环异构化反应进行了研究,这类反应具有较广的底物适应范围,在转化过程中,卤素发生了分子内转移.这类反应提供了一条新的立体选择性合成具有α-氯烯基结构的丁内酯、丁内酰胺、四氢呋喃、吡喃以及五元碳环等分子的方法.发展了两种不同的催化剂体系,即阳离子催化剂体系和中性催化剂体系.阳离子催化剂体系仅能催化顺式烯炔底物的环异构化,相反中性催化剂体系不但能催化顺反烯炔底物的环异构化,而且具有更广的底物适应范围.利用各种烯炔异构体,通过合适的控制实验对反应机理进行了研究.提出了涉及π-烯丙基铑中间体的可能机理,并且利用该机理对一些反应现象进行了解释.最后利用Suzuki偶联反应对产物进行了衍生.
The isomerization reaction of 1,6-alkynyl ring catalyzed by rhodium has been studied, which has a wide range of substrate adaptability and the intramolecular transfer of halogen occurs during the conversion. This kind of reaction provides a new , A method for the stereoselective synthesis of molecules such as butyrolactone, butyrolactam, tetrahydrofuran, pyran, and five-membered carbocycle having an α-chloroalkenyl structure, two different catalyst systems have been developed, namely a cationic catalyst system and a Catalyst system.The cationic catalyst system can only catalyze the ring isomerization of cis-alkenyne substrate, on the contrary, the neutral catalyst system can not only catalyze the ring isomerization of cis-alkenyne substrate, but also have a broader substrate adaptation The possible mechanism of the π-allyl rhodium intermediate was proposed by using various enyne isomers and the appropriate control experiments were also carried out. Some reaction phenomena were explained by using this mechanism. Finally, the product was derivatized by Suzuki coupling reaction.