Anhydrobetulin and its derivatives

Abstract

The structure of anhydrobetulin II and its derivatives I, III and IV has been solved using 1H and 13C NMR spectra, mass spectra and chemical transformations. It has been proven that in addition reactions the trisubstituted double bond is attacked selectively from the α-side under formation of D/E cis-annelated derivatives VIII, X and XI. The 22-oxo derivative XIII exhibits an anomalous Cotton effect and, in contrast to its saturated analogue XXVII,it is not epimerized in alkaline medium. Trinordiketone XXI easily epimerizes to a mixture in which the 17βH-epimer XXIb predominates, trinorketone XXIV is stable only if the annelation of rings D and E is trans. These differences are explained in terms of steric interactions of substituents in position 19. The steric course of reduction of ketones XIII and XXIV with sodium borohydride is described.