Stereoselective construction of optically active bicyclo[3.3.0]octenone derivatives based on the Pauson–Khand reaction

Abstract

A new procedure for synthesis of optically active bicyclo[3.3.0]octenone derivatives possessing two distinguishable hydroxy groups was developed based on the intramolecular Pauson–Khand reaction of optically active enynes, which were easily prepared from dimethyl L-tartrate. (4S,5S)-4,5-Bis(tert-butyldimethylsiloxy)-7-(trimethylsilyl)hept-1-en-6-yne, for example, afforded (5S,7S,8S)-7,8-bis(tert-butyldimethylsiloxy)-2-(trimethylsilyl)bicyclo[3.3.0]oct-1-en-3-one exclusively, whereas (3S,4S)-3,4-dihydroxy-7-(trimethylsilyl)hept-1-en-6-yne produced (5R,6S,7S)-6,7-dihydroxy-2-(trimethylsilyl)bicyclo[3.3.0]oct-1-en-3-one in a highly stereoselective manner.