RESUMO
The copper-catalyzed substitution reaction of diethyl phosphate derived from TMSCîCCH(OH)CH2CH2OTBDPS with 3-c-C5H9-4-MeOC6H3MgBr, followed by several transformations, afforded a tumor necrosis factor inhibitor possessing a Ph-acetylene moiety. The inhibitor was also synthesized from phenylacetylene phosphate PhCîCCH(OP(O)(OEt)2)CH2CH2OTBDPS. Furthermore, the substitution of phosphates derived from TMSCîCCH(OH)CH3 and TMSCîCCH(OH)-i-Pr with 3-F-4-PhC6H3MgBr gave the corresponding substitution products, which were transformed to flurbiprofen and its i-Pr analogue, respectively. The copper-catalyzed substitutions in these syntheses proceeded in a regio- and stereoselective manner.
Assuntos
Alcinos/química , Cobre/química , Flurbiprofeno/síntese química , Indicadores e Reagentes/química , Propanóis/química , Fator de Necrose Tumoral alfa/antagonistas & inibidores , Catálise , Flurbiprofeno/química , Flurbiprofeno/farmacologia , EstereoisomerismoRESUMO
Four optically pure isomers of dioxetane (1) were decomposed by the action of the complex of an optically active crown ether with potassium tert-butoxide to afford light with lambda(max)CL and gave four different spectrum shapes.