title: Asymmetric Synthesis of Rauhut-Currier type Products by a Regioselective Mukaiyama Reaction under Bifunctional Catalysis.
abstract: The reactivity and the regioselective functionalization of silyl-diene enol ethers under a bifunctional organocatalyst provokes a dramatic change in the regioselectivity, from the 1,5- to the 1,3-functionalization. This variation makes possible the 1,3-addition of silyl-dienol ethers to nitroalkenes, giving access to the synthesis of tri- and tetrasubstituted double bonds in Rauhut-Currier type products. The process takes place under smooth conditions, nonanionic conditions, and with a high enantiomeric excess. A rational mechanistic pathway is presented based on DFT and mechanistic experiments.
authors.affiliation: Department of Organic Chemistry (module 01), Universidad Autónoma de Madrid , Cantoblanco, 28049 Madrid, Spain.
authors.forename: María
authors.initials: M
authors.lastname: Frias
authors.affiliation: Department of Inorganic Chemistry (module 07), Universidad Autónoma de Madrid , 28049 Madrid, Spain.
authors.forename: Rubén
authors.initials: R
authors.lastname: Mas-Ballesté
authors.affiliation: División Académica de Ciencias Básicas, Universidad Juárez Autónoma de Tabasco , 86040 Villahermosa, Tabasco, Mexico.
authors.forename: Saira
authors.initials: S
authors.lastname: Arias
authors.affiliation: División Académica de Ciencias Básicas, Universidad Juárez Autónoma de Tabasco , 86040 Villahermosa, Tabasco, Mexico.
authors.forename: Cuauhtemoc
authors.initials: C
authors.lastname: Alvarado
authors.affiliation: Department of Organic Chemistry (module 01), Universidad Autónoma de Madrid , Cantoblanco, 28049 Madrid, Spain.
authors.forename: José
authors.identifier: 0000-0003-0164-1777
authors.initials: J
authors.lastname: Alemán