Total Synthesis of C30 Botryococcene and epi‐Botryococcene by a Diastereoselective Ring Opening of Alkenylcyclopropanes

Trialkylaluminum compounds perform a diastereoselective 1,6‐ring fragmentation of alkenylcyclopropane. This new tool allows the preparation of hydrocarbon compounds containing two distant stereocenters with a good diastereocontrol. Inspired by the biosynthesis of botryococcene this methodology was a...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2018-10, Vol.57 (40), p.13237-13241
Main Authors: Cormier, Morgan, de la Torre, Aurélien, Marek, Ilan
Format: Article
Language:English
Subjects:
Biosynthesis
botryococcene
carbometalation
cyclopropane
Enantiomers
organoalane
Ring opening
Stereoselectivity
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Summary:Trialkylaluminum compounds perform a diastereoselective 1,6‐ring fragmentation of alkenylcyclopropane. This new tool allows the preparation of hydrocarbon compounds containing two distant stereocenters with a good diastereocontrol. Inspired by the biosynthesis of botryococcene this methodology was applied successfully to the diastereo‐ and enantioselective preparation of this triterpene and its epimer. A novel approach was developed for the preparation of acyclic hydrocarbons bearing one quaternary and one tertiary stereocenter in a 1,4‐relationship. The method is based on the diastereoselective biomimetic ring‐opening of cyclopropane methanol derivatives using ambiphilic organoalane nucleophiles. The strategy was applied to the total synthesis of botryococcene and epi‐botryococcene.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201808709