Substrate-Controlled [8 + 3] Cycloaddition of Tropsulfimides and Tropones with Zwitterionic Allenyl Palladium Species Derived from Vinylidenecyclopropane-diesters

J Org Chem. 2024 Oct 18;89(20):14831-14850. doi: 10.1021/acs.joc.4c01579. Epub 2024 Oct 4.

Abstract

A palladium-catalyzed regioselective [8 + 3] cycloaddition of tropsulfimides and tropones with vinylidenecyclopropane-diesters (VDCP-diesters) has been disclosed in this paper, affording decahydro-1H-cyclohepta[b]pyridine derivatives bearing an allene moiety or decahydro-1H-cyclohepta[b]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.