✍ Scribed by Alexander Sudau; Winfried Münch; Jan-W. Bats; Udo Nubbemeyer
No coin nor oath required. For personal study only.
The bicyclic core of the pumiliotoxins was synthesized in nine to eleven steps starting from L-(-)-proline. This chiral pool starting material was initially converted into an optically active 2-vinylpyrrolidine by standard operations. The first key step allowed the generation of a nine-membered ring lactam by means of a zwitterionic aza-Claisen rearrangement. The 1,4 chirality transfer was found to be low, but the double bond of the azoninone was generated with an exclusive trans configuration in a planar-S arrangement. The mixture of diastereomers thus obtained was immediately epoxid-
📜 SIMILAR VOLUMES
The convergent total synthesis of pumiliotoxins by attachment of the side chain to a suitably functionalized core indolizidinone derivative has been achieved. The use of an aldoltype addition condensation strategy, intended to provide for the stereoselective generation of the exocyclic double bond,
## Abstract Die erste Totalsynthese des racemischen Alkaloids Pumiliotoxin‐C (9) ausgehend von __trans__‐1‐Brom‐3‐penten (1) wird beschrieben. Die Schlüsselstufe 6 → 7 verläuft über eine intramolekulare __Diels__‐__Alder__‐Reaktion unter weitgehender sterischer Kontrolle von vier Chiralitätszentren