Syntheses and reactions of 1-amino-2,2-dialkylcyclopropane-1-carbonitrilesand -carboxamides - Potential precursors of ACC derivatives

The direct cyclization of 2-amino-4-chloro-3,3-dimethylbutanenitrile with p otassium tert-butoxide in THF afforded 1-amino-2,2-dimethylcyclopropane-1-c arbonitrile and a dimerization product. Various new cis- and trans-1-(teri- butylamino)-2-benzyl- 2-methylcyclopropane-carbonitriles and the correspond ing cyclopropanecarboxamides have been synthesized, with focus on the isola tion of the pure stereoisomeric cyclopropanecarboxamides. The relative conf iguration of the stereoisomers was established by X-ray crystallographic an alysis of one of the model compounds. A new route to the latter functionali zed cyclopropanes was developed by reaction of 1-methoxycyclopropylamines w ith potassium cyanide. Some remarkable rearrangements of 1-aminocyclopropan e-1-carbonitriles into azetidine and oxazine derivatives via Favorskii-deri ved intermediates are reported. Various aspects of the chemistry of geminal ly functionalized cyclopropanes are discussed.