School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, U.K.
J Org Chem. 2020 Mar 20;85(6):4507-4514. doi: 10.1021/acs.joc.0c00369. Epub 2020 Mar 10.
DFT calculations on the carbocation intermediates that connect the biosynthetic pathways leading to the sand fly pheromone sobralene and taxadiene have been made. Establishment of the conformation of the macrocyclic carbocation intermediate required to produce the ()-C8,C9 alkene bond in sobralene has identified new conformations of the verticillyl carbocation intermediates on the taxadiene biosynthetic pathway. These "sobralene-like" carbocation conformations provide an exothermic pathway to taxadiene and are validated by comparison to closely related structures (X-ray and NMR).
已对连接到沙蝇信息素索布勒烯和紫杉烯生物合成途径的碳正离子中间体进行了 DFT 计算。建立产生索布勒烯中（）-C8，C9 烯键所需的大环碳正离子中间体的构象，确定了紫杉烯生物合成途径中垂直碳正离子中间体的新构象。这些“索布勒烯样”碳正离子构象为紫杉烯提供了一条放热途径，并通过与密切相关的结构（X 射线和 NMR）进行比较得到了验证。
