ORGANOMETALLIC CATALYSIS AND ITS APPLICATION TO THETOTAL SYNTHESIS

Negishi coupling has been serving as one of thepowerful methods for the construction of C-C bondsince its first discovery in 1976. Many researchgroups have utilized Negishi coupling to synthesizevarious types of natural products or complex organiccompounds as the pivotal step. To overcome along-standing synthetic challenge of preparing(Z)-trisubstituted alkenes, the author developed anovel methodology for the first time, as depicted inchapter one, which has been successfully applied tothe synthesis of discodermolide, (-)-callystatin Aand archazolid A and B natural products, and mostimportantly, to the total synthesis of(6E,10Z)-O-Methylmyxalamide D, for the first time. Asdiscussed in chapter two, a rather novel method wasprovided to prepare HZrCp2Cl, which has been employedin the synthesis of conjugated oligoenes. In Chapterthree, thanks to the combination of lipase-catalyzedacetylation and Zr catalysis, the synthetic power ofZr-catalyzed Asymmetric Carboalumniation of Alkenes(ZACA) has been eloquently demonstrated through thesynthesis of many natural products, which seem to bemission impossible if only the ZACA was used alone.