25375-38-6Relevant articles and documents
General, Auxiliary-Enabled Photoinduced Pd-Catalyzed Remote Desaturation of Aliphatic Alcohols
Parasram, Marvin,Chuentragool, Padon,Wang, Yang,Shi, Yi,Gevorgyan, Vladimir
, p. 14857 - 14860 (2017/10/31)
A general, efficient, and site-selective visible light-induced Pd-catalyzed remote desaturation of aliphatic alcohols into valuable allylic, homoallylic, and bis-homoallylic alcohols has been developed. This transformation operates via a hybrid Pd-radical mechanism, which synergistically combines the favorable features of radical approaches, such as a facile remote C-H HAT step, with that of transition-metal-catalyzed chemistry (selective β-hydrogen elimination step). This allows achieving superior degrees of regioselectivity and yields in the desaturation of alcohols compared to those obtained by the state-of-the-art desaturation methods. The HAT at unactivated C(sp3)-H sites is enabled by the easily installable/removable Si-auxiliaries. Formation of the key hybrid alkyl Pd-radical intermediates is efficiently induced by visible light from alkyl iodides and Pd(0) complexes. Notably, this method requires no exogenous photosensitizers or external oxidants.
EPIMERIC 17-HYDROXY DERIVATIVES OF 14β-ANDROST-5-EN-3β-YL ACETATE
Cerny, Ivan,Pouzar, Vladimir,Budesinsky, Milos,Drasar, Pavel,Havel, Miroslav
, p. 2510 - 2520 (2007/10/02)
A new, six-step synthesis of 3β-hydroxy-14β-androst-5-en-17-one (IX) starting from 3β-hydroxyandrost-5-en-17-one has been elaborated.Reduction of acetate X with sodium borohydride afforded 17α-hydroxy-14β-androst-5-en-3β-yl acetate (XI).The corresponding 17β-derivative XIV was obtained by epimerization of 17α-O-tosyl derivative XIII with sodium nitrite in hexamethylphosphoramide.The 13C and 1H NMR spectra of 14β-androstane derivatives are discussed.