Application of (2-Cyanoaryl)arylacetonitriles in Cyclization and Annulation Reactions. Preparation of 3-Arylindans, 4-Aryl-3,4-dihydronaphthalenes, 4-Arylisoquinolines, 1-Aminonaphthalenes, and Heterocyclic Analogues

Article abstract of DOI:10.1021/jo00303a012

(2-Cyanoaryl)arylacetonitriles, obtained from o-halogen-substituted cyanoaromatics and arylacetonitriles may be alkylated with methyl chloroacetate.Subsequent abstraction of the proton adjacent to the ester group followed by attack of the anion at the aromatic cyano group gives rise to annulated 1-aminocyclopentenes by a Dieckmann-type reaction.The homologous esters similarly produce annulated 1-aminocyclohexenes.The generality of this annulation method is demonstrated by preparation of derivatives of 1-amino-1H-indene, 4-amino-6H-cyclopentathiophene, 5-amino-7H-pyrindine, 1-amino-3,4-dihydronaphthalene, and 5-amino-2,9-dihydro-1H-cyclopentisoquinoline.Hydrolysis and decarboxylation of these compounds leads to ketones as exemplified by synthesis of 3-arylindan-1-ones and 4-aryl-3,4-dihydro-1(2H)-naphthalen-1-ones.When treated with hydrogen bromide, the (2-cyanophenyl)phenylacetonitriles cyclize to <3,4>-condensed 3-bromo-5-aryl-6-aminopyridines.Thus, derivatives of isoquinoline, thieno<3,2-c>pyridine, and 1,6-naphthyridine were prepared.