Bismuth triflate-catalyzed Wagner-Meerwein rearrangement in terpenes. Application to the synthesis of the 18alpha-oleanane core and A-neo-18alpha-oleanene compounds from lupanes.

Abstract

The use of bismuth(III) salts as catalysts for the Wagner-Meerwein rearrangement of lupane derivatives with expansion of ring E and formation of an additional O-containing ring is reported. This process has also been extended to other terpenes, such as the sesquiterpene (-)-caryophyllene oxide. When the reaction was performed with oleanonic acid, 28,13beta-lactonization occurred, without Wagner-Meerwein rearrangement. Under more vigorous reaction conditions, dehydration of the 3beta-hydroxyl group and subsequent additional Wagner-Meerwein rearrangement led to the selective synthesis of A-neo-18alpha-oleanene compounds, in very high yields.