Stereospecific alpha-methallylation of hydroxyaldehydes by silatropic ene cyclisation

We describe the thermal rearrangement of aldehydes bearing an α-(allyl- or crotylsilyl)oxy substituent. The transformations are best described mechanistically as intramolecular silatropic ene reactions based on stereoselectivity, kinetic and computed transition state data. The overall process consti...

Popoln opis

Bibliografske podrobnosti
Main Authors: Robertson, J, Hall, M, Green, S
Format: Journal article
Jezik:English
Izdano: 2009
Opis
Izvleček:We describe the thermal rearrangement of aldehydes bearing an α-(allyl- or crotylsilyl)oxy substituent. The transformations are best described mechanistically as intramolecular silatropic ene reactions based on stereoselectivity, kinetic and computed transition state data. The overall process constitutes a stereospecific (meth)allylation of α-hydroxyaldehydes, under neutral conditions, in which the hydroxyl protecting group is also the (meth)allylating agent. © 2009 Elsevier Ltd. All rights reserved.