title: Direct Conversion of Nitriles into Alkene "Isonitriles".
abstract: The sequenced addition of RLi to nitriles, trapping with isopropylformate, and dehydration with phosphoryl chloride provides an efficient, direct synthesis of alkene isocyanides. The one-pot sequence involves a series of carefully orchestrated steps: addition, formylation, tautomerization, and dehydration, with CuCN catalyzing a key equilibration of a formyl imine to an N-formyl enamine. The resulting aromatic alkeneisocyanides, that are otherwise challenging to synthesize, engage in an unusual [4+2]-type cycloaddition/1,3-H shift/decyanation sequence to afford substituted naphthalenes.
authors: Department of Chemistry, Drexel University, 32 S. 32 nd Street, Philadelphia, PA, 19104-2875, USA.
authors: Yajun
authors: Y
authors: Li
authors: Department of Chemistry, Drexel University, 32 S. 32 nd Street, Philadelphia, PA, 19104-2875, USA.
authors: Fraser F
authors: 0000-0002-9637-0246
authors: FF
authors: Fleming
mesh_terms: D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry*; D003486:Cyanides / Q000138:chemical synthesis* / Q000737:chemistry; D061565:Cycloaddition Reaction; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D003486:Cyanides; D009570:Nitriles
keywords: alkeneisocyanide; copper catalysis; isocyanide; naphthalene; nitrile