Automatic assembly of skeleton structures. 3. Stereoselective synthesis, stereochemistry, and cyclization ofd,l-?,?'-dioxy-?,?'-di-tert-butylglutaric acid

Abstract

Stereoselective synthesis of d,l-α,α′-dioxy-α,α′-di-tert-butylglutaric acid hydroxyiminolactonitrile (3) was conducted by the reaction of dipivaloylmethane with HCN in ether. The corresponding hydroxylacetonitrile (4) and amide (5), acid (6), and its ester (7), from which dilactone (8) was synthesized with preparative yields, were obtained from3. Benzyl amide (9) was obtained by the reaction of8 with BnNH2. The iminolactone structure3 of dipivaloylmethane bis-cyanohyrin, thecis-pseudo-a orientation of the functional substituents in3–7 and9, and the structure of the dilactone8 were confirmed by the1H,13C NMR,IR and mass spectra.