1218935-78-4Relevant articles and documents
Asymmetric total synthesis of vindoline
Kato, Daisuke,Sasaki, Yoshikazu,Boger, Dale L.
body text, p. 3685 - 3687 (2010/05/15)
"Chemical equation presented" A concise asymmetric total synthesis of (-)-vindoline (1) is detailed based on a tandem intramolecular [4+2]/[3+2] cycloaddition cascade of a 1,3,4-oxadiazole inspired by the natural product structure, in which the tether linking the initiating dienophile and oxadiazole bears a chiral substituent that controls the facial selectivity of the initiating Diels-Alder reaction and sets absolute stereochemistry of the remaining six stereocenters in the cascade cycloadduct. This key reaction introduces three rings and four C-C bonds central to the pentacyclic ring system setting all six stereocenters and introducing essentially all the functionality found in the natural product in a single step. Implementation of the approach also required the development of a unique ring expansion reaction to provide a six-membered ring suitably functionalized for introduction of the .(6, 7)-double bond found in the core structure of vindoline and defined our use of a protected hydroxymetyl group as the substituent used to control the stereochemical course of the cycloaddition cascade.
