Steroids as chiral model compounds for selective reactions with metals

Our own work on steroid compounds with defined conformation as chiral model compounds for investigations of chemo-, regio- and stereoselectivity of metal-mediated new reactions is reviewed. Reactions with nickelacycles, (π-allyl)zirconoxycarbene complexes, iron tricarbonyl complexes of dienes and 1-azadienes, the Ru-catalyzed synthesis of 1,3-dihydropyrrol-2-ones from 1-azadienes, the Pd-catalyzed cyclopropanation of 1-azadienes, syntheses with cuprio steroids, copper complexes of amino alcohol derivatives and the copper-mediated hydroxylation of nonactivated C–H bonds with molecular oxygen are discussed.