title: Synthesis of Vinyl Isocyanides and Development of a Convertible Isonitrile.
abstract: The reaction of isocyanomethylenetriphenylphosphorane, generated in situ from the corresponding phosphonium salt, with a diverse set of aldehydes afforded vinyl isocyanides in good to high yields. Excellent E-selectivity was observed for aliphatic aldehydes and 2,6-disubstituted aromatic aldehydes, whereas Z-olefins were formed predominantly with ortho-substituted aryl aldehydes. (Z)-1-Bromo-2-(2-isocyanovinyl)benzene (5l) was found to be a truly universal isonitrile since, after Ugi reaction, the resulting secondary amide unit (RNHCO-) is convertible under both acidic and basic conditions. The application of 5l in the synthesis of polyheterocycles is also illustrated.
authors.affiliation: Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne , EPFL-SB-ISIC-LSPN, BCH 5304, 1015 Lausanne, Switzerland.|Department of Chemistry and Industrial Chemistry, University of Genova , Via Dodecaneso 31, 16146 Genova, Italy.
authors.forename: Martina
authors.initials: M
authors.lastname: Spallarossa
authors.affiliation: Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne , EPFL-SB-ISIC-LSPN, BCH 5304, 1015 Lausanne, Switzerland.
authors.forename: Qian
authors.initials: Q
authors.lastname: Wang
authors.affiliation: Department of Chemistry and Industrial Chemistry, University of Genova , Via Dodecaneso 31, 16146 Genova, Italy.
authors.forename: Renata
authors.initials: R
authors.lastname: Riva
authors.affiliation: Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne , EPFL-SB-ISIC-LSPN, BCH 5304, 1015 Lausanne, Switzerland.
authors.forename: Jieping
authors.initials: J
authors.lastname: Zhu