分子内Ｈｅｃｋ反応による４級炭素の触媒的不斉構築 合成手法としての発展と反応機構の探究

Abstract

Within the last decade, the enormous synthetic potential of the Heck reaction has been revealed. When employed intramolecularly, Heck reactions succeed in even forming quaternary carbon centers. The ability of intramolecular Heck reactions to reliably fashion carbon-carbon bonds in polyfunctional molecules has led to wide application of this reaction at the strategy level for the synthesis of complex natural products. One of the most important developments in this area is the increasing success being realized in effecting catalytic asymmetric Heck reactions using enantiopure ligands. Although only modest enantiocontrol was achieved in early stages, many asymmetric Heck reactions have now been demonstrated that proceed with >90% ee. Another development of the Heck reaction has led to greater understanding of its mechanistic details with two distinct pathways, the neutral and cationic pathways, being recognized. This review summarizes the synthetic developments of the intramolecular asymmetric Heck reaction for forming quaternary carbon centers and the mechanistic factors recently revealed to effect enantioselectiv- ity.