Stereocontrolled total synthesis of (+/-)-gelsemine
Abstract
Gelsemine (1) has been recognized as the major alkaloid component of Gelsemium sempervirens since 1870. It has attracted numerous synthetic efforts since the 1960s due to its unique rigid, hexacyclic cage structure. The first completely stereocontrolled total synthesis of gelsemine (1) via 21-oxogelsemine (3) is described herein. This synthesis features a stereospecific condensation between cyclopropyl carboxaldehyde (240) and 4-iodo-oxindole (259), facile construction of the tetracyclic intermediate (262) through a novel application of divinylcyclopropane-cycloheptadiene rearrangement, and an unprecedented silver-mediated cyclization between carbamoyl chloride and ene-carbamate.(UNFORMATTED TABLE OR EQUATION FOLLOWS)$$\vbox{\vskip108pt}$$(TABLE/EQUATION ENDS)
Description
Advisor
Degree
Type
Keywords
Citation
Liu, Gang. "Stereocontrolled total synthesis of (+/-)-gelsemine." (1996) Diss., Rice University. https://hdl.handle.net/1911/16928.