ORGANOMETALLIC CATALYSIS AND ITS APPLICATION TO THE TOTAL SYNTHESIS

Negishi coupling has been serving as one of the§powerful methods for the construction of C-C bond§since its first discovery in 1976. Many research§groups have utilized Negishi coupling to synthesize§various types of natural products or complex organic§compounds as the pivotal step. To overcome a§long-standing synthetic challenge of preparing§(Z)-trisubstituted alkenes, the author developed a§novel methodology for the first time, as depicted in§chapter one, which has been successfully applied to§the synthesis of discodermolide, (-)-callystatin A§and archazolid A and B natural products, and most§importantly, to the total synthesis of§(6E,10Z)-O-Methylmyxalamide D, for the first time. As§discussed in chapter two, a rather novel method was§provided to prepare HZrCp2Cl, which has been employed§in the synthesis of conjugated oligoenes. In Chapter§three, thanks to the combination of lipase-catalyzed§acetylation and Zr catalysis, the synthetic power of§Zr-catalyzed Asymmetric Carboalumniation of Alkenes§(ZACA) has been eloquently demonstrated through the§synthesis of many natural products, which seem to be§mission impossible if only the ZACA was used alone.