Revised Structure of Tolyporphin A

Four monocyclic precursors were assembled in the total synthesis of the proposed structure 1 - A of (+)-tolyporphin A O,O-diacetate (X=Ac). Comparison of the spectroscopic data demonstrated that synthetic tolyporphin O,O-diacetate did not match the O,O-diacetate prepared from natural (+)-tolyporphin A (X=H), calling for a structural revision of this class of natural products. On the basis of a series of NMR experiments including synthetic intermediates, the structure of tolyporphin A is concluded to be 1 - B , in which the configurations of quaternary centers C7 and C17 are opposite to those in the originally proposed structure.