A domino [4+2]/retro [4+2] cycloaddition process of cyclohexadienes with arylethynes or benzyne providing access to biaryls and polycyclic aromatics has been studied theoretically using density functional theory calculations. It has been found that the initial Diels-Alder (D-A) reaction acts as the rate-determining step and the consequent [4+2] cycloreversion reaction is feasible under the conditions used. Furthermore, the D-A reaction affects the regioselectivity, the origin of which is essentially derived from the good match of orbital coefficients between dienes and dienophiles as shown by using frontier molecular orbital (FMO) theory. Further investigation of the reactivity reveals that the reactions are predicted to fail to occur if an electron-donor group in the diene or an electron-acceptor group in the dienophile is lacking, as a consequence of the increased FMO energy gap. By further exploring the scope of substrates computationally, benzyne as an active dienophile was predicted to react with a variety of dienes in a cascade reaction under mild conditions with a low energy barrier, with the rate-determining step being the retro [4+2] cycloaddition.
A series of trans-3-chloro-β-lactams was synthesized stereospecifically from imines and chloroacetyl chloride or a mixture of chloroacetyl chloride and nitroacetyl chloride, prepared from vinylidene chloride and a mixture of concentrated nitric acid and sulfuric acid, in the presence of triethylamine. The reaction of vinylidene chloride and the mixed acid was investigated. The formation mechanism of chloroacetyl chloride and nitroacetyl chloride and their reaction process with imines were proposed.
4-Acyl-β-lactams are important synthetic intermediates in both pharmaceutical and organic chemistry. Cis- and trans-4-acyl-β- lactams were synthesized stereoselectively from vicinal diketones via the formation of bulky and less bulky diimines as key intermediates, respectively. The diimines reacted with acyl chloride in the presence of triethylamine to give rise to the corre- sponding 4-imino-β-lactams, which were further hydrolyzed to afford 4-acyl-β-lactams. The cis- and trans selectivity is de- pended on the steric hindrance of the imine N-substituents. A series of cis-4-acyl-β-lactams were synthesized from vicinal ketoaldehydes via the formation of their monoimines and diimines as intermediates. Pyruvic aldehyde produced cis-4-acetyl-β- lactams and cis-4-formyl-β-lactams, respectively, through the reactions of its monoimine and diimine with acyl chlorides. Phenylglyoxal generated cis-4-benzoyl-β-lactams via its monoaldimine.
WANG ZhiXin & XU JiaXi*State Key Laboratory of Chemical Resource Engineering
