Long Yong-Jie, Shen Jia-Hao, Wei Yin, Shi Min
State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, University of Chinese Academy of Sciences, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, People's Republic of China.
J Org Chem. 2024 Oct 18;89(20):14831-14850. doi: 10.1021/acs.joc.4c01579. Epub 2024 Oct 4.
A palladium-catalyzed regioselective [8 + 3] cycloaddition of tropsulfimides and tropones with vinylidenecyclopropane-diesters (VDCP-diesters) has been disclosed in this paper, affording decahydro-1-cyclohepta[]pyridine derivatives bearing an allene moiety or decahydro-1-cyclohepta[]pyran derivatives having a conjugated diene unit in moderate to good yields. The reactions proceed through a zwitterionic allenyl palladium species derived from VDCP-diesters. The substrate scopes have been investigated and the plausible reaction mechanisms have also been proposed according to the previous work, the first captured zwitterionic Pd-allenyl intermediate, and control experiments.
本文报道了钯催化的特罗普磺酰亚胺和环庚三烯与亚乙烯基环丙烷二酯（VDCP-二酯）的区域选择性[8 + 3]环加成反应，以中等至良好的产率得到含有丙二烯部分的十氢-1-环庚并[]吡啶衍生物或具有共轭二烯单元的十氢-1-环庚并[]吡喃衍生物。反应通过由VDCP-二酯衍生的两性离子烯丙基钯物种进行。根据先前的工作、首次捕获的两性离子钯-烯丙基中间体以及对照实验，研究了底物范围并提出了合理的反应机理。
