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)
| Identifer | oai:union.ndltd.org:RICE/oai:scholarship.rice.edu:1911/16928 |
| Date | January 1996 |
| Creators | Liu, Gang |
| Contributors | Fukuyama, T. |
| Source Sets | Rice University |
| Language | English |
| Detected Language | English |
| Type | Thesis, Text |
| Format | 222 p., application/pdf |
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