1988 年 46 巻 4 号 p. 367-377
Contrary to the firm and long-standing credence on the involvement of racemization, the “cationic” 1, 2-rearrangement reactions may proceed stereospecifically under suitable reaction conditions to allow the complete 1, 2-chirality transfer. This fact provides a solid basis for the development of a novel and useful synthetic reactions to achieve the highly selective acyclic steoeocontrol. This paper deals with a survey of the new synthetic methodology based on the novel 1, 2-rearrangements under Lewis acidic conditions as well as the newly exploited silicon-directed relative streocontrol, which would find a broad applicability in the highly stereoselective synthesis of a wide variety of useful compounds including chiral pheromones, macrolides, and so on.