Lignans and related phenols. Part XV. Remote substituent effects on the rates and products of some reactions of aryltetrahydronaphthalenes

Abstract

An unambiguous example of the steric acceleration of a simple solvolysis at an uncongested site by a remote substituent is given. Other evidence of remote control of product formation has been obtained and related to the design of cancer-inhibitory podophyllotoxins. The findings have been applied to the synthesis of a peltatin (VII) which is stable and physiologically active in both acid and alkaline media. Evidence of extreme compression, ready extrusion of substituents, and encagement of other molecules is presented.