Stereoselective radical aryl migration from silicon to carbon.
Highly diastereoselective radical 1,5 phenyl migration reactions from silicon in diarylsilyl ethers to various C-centered radicals to form the corresponding 3-phenylated alcohols are described. Functionalized aryl groups can also be transferred. The effect of the variation of the attacking radical on the aryl transfer reaction is discussed. Best results are obtained for the phenyl migration to nucleophilic secondary alkyl radicals, where high yields (up to 81%) and high selectivities (up to 95% ds) have been obtained. The mechanism of the process is discussed and a model to explain the stereochemical outcome of the reaction is presented. Finally, stereoselective 1,4 aryl migration reactions from Si to C, including a new method for the alpha-arylation of esters, are presented.
Amrein
S
S
Laboratorium für Organische Chemie, Eidgenössische Technische Hochschule, ETH Zentrum, Zürich, Switzerland.
Bossart
M
M
Vasella
T
T
Studer
A
A
D000438:Alcohols / Q000138:chemical synthesis / Q000737:chemistry*; D000478:Alkylation; D002244:Carbon; D004987:Ethers / Q000737:chemistry*; D010636:Phenols / Q000737:chemistry*; D012825:Silicon / Q000737:chemistry*; D013237:Stereoisomerism
D000438:Alcohols; D004987:Ethers; D010636:Phenols; D002244:Carbon; D012825:Silicon