Rearrangements and Hydration of 2-Ethynylisoborneol and 2-Ethynylisocamphanol

Abstract

The reaction of 2-ethynylisoborneol with acetic acid in the presence of boron trifluoride-diethyl ether complex gave 4-ethynylisobornyl acetate as a result of successive skeletal rearrangements. Under the Kucherov reaction conditions 2-ethynylisoborneol underwent Meyer—Schuster rearrangement leading to (2-bornylidene)acetaldehyde. The hydration product of 2-ethynylisoborneol, 2-acetylisoborneol, was obtained by the action of mercury(II) acetate in dioxane under mild conditions. The Nieuwland reaction of 2-ethynylisoborneol afforded 4-acetylisoborneol acetate. 2-Ethynylisocamphanol in the presence of formic acid gave rise to a mixture of Rupe and Meyer—Schuster rearrangement products, stereoisomeric 2-(isocamphylidene)acetaldehydes and 2-acetylisocamphene. Mixtures of acetyl-substituted acetates having a camphane, isocamphane, and bicyclo[3.2.1]octane skeleton were obtained in the reaction with acetic acid in the presence of BF3-Et2O. Under the Nieuwland reaction conditions 2-ethynylisocamphanol underwent hydration and rearrangement with ring expansion, yielding a mixture of endo-2-hydroxy-2,6,6,7-tetramethylbicyclo[3.2.1]octan-3-one and the corresponding acetate.