The role of the 12-carboxylic acid group in the spontaneous autoxidation of dihydroartemisinic acid
摘要:
Three of the four steps in the slow spontaneous autoxidation of dihydroartemisinic acid to artemisinin ('ene-type' reaction of molecular oxygen with the Delta(4.5) double bond, Hock cleavage of the resulting tertiary allylic hydroperoxide, oxygenation of the enol product from Hock cleavage and cyclization of the resulting vicinal hydroperoxyl-aldehyde to the 1,2,4-trioxane system of artemisinin) are shown to be assisted by the proximity of the 12-carboxylic acid functional group in dihydroartemisinic acid to the functional groups participating in these reactions. (C) 2002 Elsevier Science Ltd. All rights reserved.
作者:Vishunu S Shukla、Nabin C Barua、Pritish K Chowdhury、Ram P Sharma、Manobjyoti Bordoloi、Urszula Rychlewska
DOI:10.1016/s0040-4020(01)87521-9
日期:1986.1
cadinenes a, a, b, a & and a degraded cadinene a whose stereostructures are presented in this paper. The absolute stereochemistry of the major component a has been determined by application of Horeau's method as well as chemical correlation studies and has been confirmed by X-ray analysis of f thus suggesting that it belongs to the amorphane group.