Semipinacol Rearrangement Reaction And Its Application In The Synthese

Construction of quaternary carbon is a challenge in organic synthesis, semipinacol rearrangement reaction as one of effective methodologies for building quaternary carbon center attracted more and more attention. In this thesis, we develop two kinds of methodologies by using semipinacol rearrangement reaction toward construction of the core skeletons of natural products that containing quaternary carbon center.In the first part, chapter 1:The history and related synthetic strategies of marine natural product (±)-halichlorineis briefly summarized; chapter 2:A tandem cyclization/semipinacol rearrangement reaction for the construction of 6-aza/oxa-spiro[4.5] decane skeletonsis developed, and its potential utility was demonstrated by a formal synthesis of the biologically active marine alkaloid (±)-halichlorine.In the second part, chapter 3:The related synthetic background of herbertane-type aromatic sesquiterpeneis reviewed; chapter 4:A catalytic asymmetric semipinacol rearrangement reaction for the construction of the core skeletons of herbertane-type sesquiterpeneis developed, then a series of benzylic a-Quaternary cycloalkanones which contain the structural motif of chiral all-carbon quaternary stereocenter are synthed in excellent enantioselectivity (up 96.5% ee). Notely, its utility was demonstrated by a total synthesis of (-)-herbertene-1,14-diol.