jo9520607_si_001.pdf (897.17 kB)
Download file

Reactivity of N-Phenyl-1-Aza-2-Cyano-1,3-Butadienes in the Diels−Alder Reaction

Download (897.17 kB)
journal contribution
posted on 31.05.1996, 00:00 authored by Nicholas J. Sisti, Irina A. Motorina, Marie-Elise Tran Huu Dau, Claude Riche, Frank W. Fowler, David S. Grierson
It is found that N-phenyl-2-cyano-1-azadiene 4, prepared via a two-step, one-pot, sequence from acrylanilide, undergoes efficient [4 + 2] cycloaddition with a complete range of electron rich, electron poor, and neutral dienophiles under remarkably mild thermal conditions (90−120 °C for 20−48 h). Regiospecific formation of the α-cycloadduct wherein the dienophile substituent is α to nitrogen is observed for vinyl ethers and styrene, whereas the Diels−Alder reactions with methyl acrylate and methyl vinyl ketone (MVK) produce α/β mixtures in which the α-cycloadduct is the major regioisomer (approximately 4−5:1). An essentially identical reaction pattern was observed in the Diels−Alder reaction of N-(p-methoxyphenyl)-2-cyano-1-azadiene 18 and the 4-methyl-substituted azadiene 27. For compound 19 derived from cycloaddition of 18 with ethyl vinyl ether, facile conversion to the dihydropyridine 21 through loss of EtOH on brief acid treatment was also noted. The 2,4-cis-disubstitution pattern confirmed by X-ray diffraction for the major cycloadduct 29 isolated from the reaction of 27 with styrene provides evidence for the endo mode of cycloaddition in the Diels−Alder reaction of N-phenyl(aryl)-2-cyano-1-azadienes. Calculation of the frontier orbital energies and coefficients, as well as the transition state geometries for the [4 + 2] cycloaddition of N-phenyl-2-cyano-1-azadiene 4 with methyl vinyl ether, styrene, and MVK were carried out at the RHF AM1 level (MOPAC, Version 5.0). The FMO treatment indicates that the reaction of 4 with methyl vinyl ether occurs under LUMOdiene control, whereas in contrast, the corresponding cycloaddition with MVK occurs preferably under HOMOdiene control. A high degree of asynchronicity is observed in the calculated transition states for reaction of 4 with the three representative dienophiles. In all cases the transition states leading to the α-cycloadducts are lower in energy than those giving the β-products. However, at the AM1 level the exo cycloaddition mode is found to be the preferred, this result contrasting with experimental results for azadiene 27.

History