CATALYTIC, ASYMMETRIC, INTRAMOLECULAR CARBON-HYDROGEN INSERTION

摘要

Among the most synthetically attractive methods for replacement of hydrogen on carbon are those that form new C-C bonds and, among these methods, controlled insertion of a metallo-carbene into a C-H bond has broad applications. This strategy has become popular, in large part, due to advances in our understanding of metallo-carbene chemistry and the evolution of its catalytic applications1"21 over the past sixty years from an impractical curiosity to a useful strategy in synthetic organic chemistry intramolecular reactions of metallo-carbenes with remote C-H bonds were the first to be investigated as synthetic strategies; they provide access to more complex materials by selective functionalization at a normally unreactive C-H site (e.g. Eq. 1) Site- and stereoselective discrimination among the C-H bonds found in complex molecules is critical to the ultimate success of these strategies. Advances in the development and applications of catalyst systems that selectively insert a carbene into a specific C-H bond have been the subject of intensive investigations,and the intramolecular applications of this method are the subject of this chapter.