Investigation of palladium(IV) species in organic synthesis and synthetic studies towards meloyunnanine A

This dissertation addresses two research themes in modern organic synthesis. The first topic explores the development of new reactions enabled by Pd(IV)-involved catalytic cycles. The second theme investigates the synthetic studies towards total synthesis of meloyunnanine A. Our group recently disclosed a first example of a catalytic dyotropic rearrangement of Pd(IV) species, representing a novel approach to activating Câ C bonds. In chapter 1, we describe the general background of Pd(IV) chemistry and our efforts to identify other examples involving the novel migration of Câ Pd(IV) bonds in domino reactions. (1) Firstly, a dyotropic rearrangement in a domino process initiated by β-C(sp3)â H bond activation of amides bearing a quaternary carbon was investigated. A broad range of saturated morpholine amides was converted to α,β-unsaturated amides as an outcome of editing their quarternary carbons. Mechanistically, it is noteworthly that the domino process contained an unprecedented 1,3-Pd(IV) shift. (2)