Regioselective Aliphatic Retro-[1,4]-Brook Rearrangements

摘要

The migration of silicon is a ubiquitous process in reactions,and the Brook rearrangement is an intramolecular migration of a silicon atom from a carbon to an oxygen atom.The reverse process-migration of a silicon atom from an oxygen to a carbon atom-is referred to as the retro-or reverse-Brook rearrangement and is a common occurrence.Studies on retro-[1,2]-Brook rearrangements have revealed that the rearrangement is highly stereospecific with regard to the configuration at the carbon atom and proceeds with retention of configuration in the alpha-silyloxy carbanions generated from aliphatic substrates,whereas inversion is observed for ben-zylic and allylic carbanions.