title: Stereospecific Synthesis of α-Amino Allylsilane Derivatives through a [3,3]-Allyl Cyanate Rearrangement. Mild Formation of Functionalized Disiloxanes.
abstract: An efficient asymmetric synthesis of α-amino allylsilane derivatives is reported. The strategy is based on a [3,3]-allyl cyanate sigmatropic rearrangement from enantioenriched γ-hydroxy alkenylsilyl compounds. The isocyanate intermediate can be trapped by several nucleophiles, opening the way for the preparation of unknown chiral functionalized compounds such as the α-ureido allylsilanes as well as carbamate derivatives. A computational study was conducted to rationalize the complete 1,3-chirality transfer of this kind of rearrangement. Moreover, starting from products bearing a phenyldimethyl silyl substituent, the α-amino silane derivatives or the corresponding disiloxanes can be obtained under hydrogenation conditions in an exclusive way according to the used catalyst.
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1 , 263, avenue du Général Leclerc, Campus de Beaulieu, Bâtiment 10A, 35042 Cedex Rennes, France.
authors.forename: Sylvain
authors.initials: S
authors.lastname: Henrion
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1 , 263, avenue du Général Leclerc, Campus de Beaulieu, Bâtiment 10A, 35042 Cedex Rennes, France.
authors.forename: Bertrand
authors.initials: B
authors.lastname: Carboni
authors.affiliation: Departamento de Química Orgánica I and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Química, Universidad del País Vasco/Euskal Herriko Unibertsitatea (UPV/EHU) and Donostia International Physics Center (DIPC) , PO Manuel Lardizabal 3, 20018 San Sebastián/Donostia, Spain.
authors.forename: Fernando P
authors.initials: FP
authors.lastname: Cossío
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1 , 263, avenue du Général Leclerc, Campus de Beaulieu, Bâtiment 10A, 35042 Cedex Rennes, France.
authors.forename: Thierry
authors.initials: T
authors.lastname: Roisnel
authors.affiliation: VillaPharma Research, Parque Tecnológico de Fuente Álamo , Ctra El Estrecho-Lobosillo, Av. Azul, E-30320, Murcia, Spain.
authors.forename: Jose M
authors.initials: JM
authors.lastname: Villalgordo
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1 , 263, avenue du Général Leclerc, Campus de Beaulieu, Bâtiment 10A, 35042 Cedex Rennes, France.
authors.forename: François
authors.initials: F
authors.lastname: Carreaux