Stereocontrolled Synthesis of Spiroketals via Ti(Oi-Pr)-Mediated Kinetic Spirocyclization of Glycal Epoxides with Retention of Configuration.

The article discusses the stereocontrolled synthesis of spiroketals. It is observed that alternate nonchelated mechanisms are inconsistent with the observed stereochemical preference. Kinetic spiroketalization is Mediated cyclization of Ti(Oi-Pr)4 and MeOH-induced cyclization (C1-inversion) provide...

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Publicado en:Journal of the American Chemical Society Vol. 128; no. 6; pp. 1792 - 1794
Autores principales: Moilanen, Sirkka B., Potuzak, Justin S., Tan, Derek S.
Formato: Artículo
Publicado: American Chemical Society 2/15/2006
Materias:
Acceso en línea:Ver este registro en EBSCOhost
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        20080004
        10.1021/ja057908f
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        atl: Stereocontrolled Synthesis of Spiroketals via Ti(Oi-Pr)-Mediated Kinetic Spirocyclization of Glycal Epoxides with Retention of Configuration.
      aug:
        au:
          Moilanen, Sirkka B.
          Potuzak, Justin S.
          Tan, Derek S.
        affil:
          Tri-Institutional Training Program in Chemical Biology.
          Pharmacology Program Weill Graduate School of Medical Sciences of Cornell University.
          Tri-Institutional Research Program and Molecular Pharmacology & Chemistry Program, Memorial Sloan-Kettering Cancer Center, 1275 York Avenue, Box 422, New York, New York.
      su:
        Chemical kinetics
        Ring formation (Chemistry)
        Reaction mechanisms (Chemistry)
        Occlusal adjustment
        Chemical reactions
        Substitution reactions
      sug:
        subj:
          Chemical kinetics
          Ring formation (Chemistry)
          Reaction mechanisms (Chemistry)
          Occlusal adjustment
          Chemical reactions
          Substitution reactions
      ab: The article discusses the stereocontrolled synthesis of spiroketals. It is observed that alternate nonchelated mechanisms are inconsistent with the observed stereochemical preference. Kinetic spiroketalization is Mediated cyclization of Ti(Oi-Pr)4 and MeOH-induced cyclization (C1-inversion) provide comprehensive access to systematically stereochemically diversified spiroketals. The exposure of the inversion spiroketal to the reaction conditions did not result in equilibration which shows that Ti(Oi-Pr)4-mediated spirocyclization is, kinetically controlled. Reduced stereoselectivity was observed when substoichiometric amounts of Ti(Oi-Pr)4 was used suggesting that the metal may remain coordinated to the product , although the complex is not responsible for the stereochemical outcome of the kinetically reaction.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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