Ylidenenorbornadiene Carboxylates: Experimental Kinetic Analysis of a Nucleophile-Induced Fragmentation Reaction
Ylidenenorbornadiene Carboxylates: Experimental Kinetic Analysis of a Nucleophile-Induced Fragmentation Reaction
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DOI：
10.1021/acs.orglett.2c00630
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发表时间：
2022-04-22
期刊：
影响因子：
5.2
通讯作者：
Bercovici，Daniel A.
中科院分区：
文献类型：
--
作者：
Malouf，David M.;Richardson，Abigail D.;Bercovici，Daniel A.
乙二烯(YNDs)是由富烯和乙炔羧酸盐之间的[4+2]环加成反应得到的，它与β-巯基乙醇反应生成四种非对映异构体的混合物。这四个非对映异构体以不同的速率通过反向[4+2]环加成反应来裂解。一种模拟的动力学方法从观察到的速率数据外推了非对映异构体的速率常数。YND在裂解速率上表现出很大的变异性，这取决于Ylidene取代基的立体电子学。含有一种羧酸酯的底物对裂解非常稳定。
Ylidenenorbornadienes (YNDs), prepared by [4 + 2] cycloadditions between fulvenes and acetylene carboxylates, react withbeta-mercaptoethanol to yield a mixture of four diastereomers. These four diastereomers fragment via a retro-[4 + 2] cycloaddition at differing rates. A simulated kinetics approach extrapolated the rate constants of the diastereomers from the observed rate data. YNDs display wide variability in rate of fragmentation, dependent on the stereoelectronics of the ylidene substituents. A substrate containing one carboxylic ester proved exceptionally stable to fragmentation.