Acid-catalyzed Rearrangement of Epoxy Alcohol Derivatives Having the Electron-withdrawing Protective Groups (Acyl or Sulfonyl): Asymmetric Synthesis of Chiral Quaternary Carbon and Spiro Centers and Its Application to Natural Products Synthesis.

Rearrangements of 1, 2-epoxy alcohol derivatives having electron-withdrawing protective groups such as acyl or sulfonyl group have been developed leading to the asymmetric construction of chiral quaternary carbon centers and spiro centers. The success of the novel rearrangements here depends on the electron-withdrawing property of the protective groups. The methods were applied to the asymmetric syntheses of several natural products such as fredericamycin A, (+) - (S) -sporochnol A, (-) -aphanorphine, and (-) -a-herbertenol.