RESUMEN
A novel persulfate-mediated oxidative glycosylation system using p-methoxyphenyl (PMP) glycosides as bench-stable glycosyl donors is developed. This study shows that both K2S2O8 as an oxidant and Hf(OTf)4 as a Lewis acid catalyst play important roles in the oxidative activation of the PMP group into a potential leaving group. This convenient glycosylation protocol proceeds under mild conditions and delivers a wide range of biologically and synthetically valuable glycoconjugates, including glycosyl fluorides.
RESUMEN
The three-component alkylfluorination of olefins via an oxidative radical-polar crossover under visible light-induced photocatalysis is disclosed. A key feature of this reaction is the incorporation of two synthetically meaningful components involving a three-dimensional alkyl group and a fluorine atom using easily preparable N-hydroxyphthalimide esters as the alkyl donors and a low-cost hydrogen fluoride as the fluorine source. Furthermore, a one-step procedure using commercially available carboxylic acids demonstrated the versatility of this new method.
Asunto(s)
Alquenos , Flúor , Catálisis , Estructura Molecular , Estrés OxidativoRESUMEN
Pladienolides, an emerging class of naturally occurring spliceosome modulators, exhibit interesting structural features, such as highly substituted 12-membered macrocycles and epoxide-containing diene side chains. The potential of pladienolides as anti-cancer agents is confirmed by H3B-8800, a synthetic analog of this natural product class, which is currently under Phase I clinical trials. Since its isolation in 2004 and the first total synthesis in 2007, a dozen total syntheses and synthetic approaches toward the pladienolide class have been reported to date. This review focuses on the eight completed total syntheses of naturally occurring pladienolides or their synthetic analogs, in addition to a synthetic approach to the main framework of the natural product.