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DOI: 10.1055/s-0042-1752540
Total Synthesis of (±)-Talatisamine
The Total Synthesis of Racemic Talatisamine.
Pure Appl. Chem. 1975;
41: 93-112
DOI: 10.1351/pac197541010093.
Total Synthesis of Talatisamine, a Delphinine Type Alkaloid.
J. Am. Chem. Soc. 1974;
96: 4990-4992
DOI: 10.1021/ja00822a048.
Key words
(±)-talatisamine - Diels–Alder reaction - [2+2] photo-cycloaddition - Lemieux–Johnson oxidation - retro-aldol–aldol reaction - Wagner–Meerwein rearrangement - aza-Prins reaction
Significance
(–)-Talatisamine is a potassium ion channel inhibitor isolated from an aconitum species. Wiesner and co-workers reported the first total synthesis of (±)‑talatisamine. Its preparation was facilitated by synthetic studies on degradation products of natural (–)-talatisamine. Other diterpene alkaloids prepared by the Wiesner group include atisine and napelline.
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Comment
The tricyclic core of (±)-talatisamine is assembled by a Diels–Alder reaction. Ring expansion from the cyclobutane in E via retro-aldol– aldol reaction furnishes the bicyclo[2.2.2]octane motif within F. The atisine-type scaffold G is converted into the delphinine-type skeleton I by Wagner–Meerwein rearrangement in analogy to Wiesner’s biosynthetic proposal. An oxidation followed by aza-Prins reaction furnishes the hexacyclic 6/6/5/6/5/6-membered-ring scaffold of (±)-talatisamine.
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Publication History
Article published online:
11 May 2023
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