| Abstract
| - The total synthesis of (±)-gelsemine (1) is described. A defining phase of the effort involvedrecourse to a strategic oxetane ring (see compound 25). It was constructed anticipating an intramoleculardisplacement of the carbon (C17)−oxygen (O4) bond (see product 48). A key intermediate in thestereospecific elaboration of the oxetane linkage was enone 22, which was susceptible to two β-face attacksleading to 24 and, thence, 25. Three sigmatropic rearrangements were employed in building the bridgehead(C20) and the spiroanilide (C7) quaternary centers en route to gelsemine.
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