Abstract
The systematic arrangement of a two-carbon unit, hydrogen atom, and oxygen atom on the versatile enal moiety of a non-natural synthetic intermediate successfully led to the unified access to the gelsedine-type alkaloids. The development and use of this new synthetic hub and an array of site-selective transformations resulted in the asymmetric synthesis of (-)-gelsenicine, (-)-gelsedine, (-)-gelsedilam, (-)-14-hydroxygelsenicine, and (-)-14,15-dihydroxygelsenicine.
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