Synthetic Studies towards Pyrido[1,2-a]azepine Stemona Alkaloids

Abstract

The carbon skeleton of the Stemona alkaloids stemokerrin and cochinchistemonine was assembled from three building blocks (a piperidine, a furan, and a tetronate). Key steps linking the fragments included a Stille cross-coupling (piperidine/furan) and an aldol-type addition of a tetronate. The furan served as a latent 1,4-difunctional compound which was converted into a γ-ketolactone by a type II photooxygenation. Attempts to construct the C12–C13 double bond of stemokerrin by a late-stage oxidation or by an elimination remained unsuccessful. The non-natural products dihydrostemokerrin and furostemokerrin were obtained instead.

Key words

alkaloids - cross-coupling - diastereoselectivity - oxidation - pyridines - total synthesis

Publication History

Received: 19 January 2022

Accepted: 21 February 2022

Accepted Manuscript online:
21 February 2022

Article published online:
23 March 2022

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