title: Retro-Brook Rearrangement of Ferrocene-Derived Silyl Ethers.
abstract: An intramolecular Li-Si exchange was observed on various lithiated ferrocenylbenzyl silyl ethers. The thermodynamically more stable C-silylated isomers were isolated in good yields and fully characterized. The reaction mechanism of the [1,4] retro-Brook rearrangement was investigated by DFT calculations. Two distinct reaction routes were proposed and a possible stabilization effect of the ferrocenyl fragment on the C-silylated isomers was described. The diastereoselective rearrangement of the trimethylsilyl group to the ortho position of the ferrocenyl cyclopentadienyl ring was also accomplished and the absolute configuration of the product was determined.
authors.affiliation: Comenius University in Bratislava, Faculty of Natural Sciences, Department of Organic Chemistry, Mlynska dolina, Ilkovičova 6, CH-2, 842 15 Bratislava (Slovakia).
authors.forename: Vladimír
authors.initials: V
authors.lastname: Bariak
authors.affiliation: Comenius University in Bratislava, Faculty of Natural Sciences, Department of Organic Chemistry, Mlynska dolina, Ilkovičova 6, CH-2, 842 15 Bratislava (Slovakia).
authors.forename: Andrea
authors.initials: A
authors.lastname: Malastová
authors.affiliation: Comenius University in Bratislava, Faculty of Natural Sciences, Department of Organic Chemistry, Mlynska dolina, Ilkovičova 6, CH-2, 842 15 Bratislava (Slovakia). ambroz.almassy@fns.uniba.sk.
authors.forename: Ambroz
authors.initials: A
authors.lastname: Almássy
authors.affiliation: Comenius University in Bratislava, Faculty of Natural Sciences, Department of Organic Chemistry, Mlynska dolina, Ilkovičova 6, CH-2, 842 15 Bratislava (Slovakia). radovan.sebesta@fns.uniba.sk.
authors.forename: Radovan
authors.initials: R
authors.lastname: Šebesta
keywords: carbanions; ferrocene; organosilanes; rearrangement; silyl transfer