Regioselective copper(i) iodide-catalyzed cycloadditions of chiral pyrazolidin-3-on-1-azomethine imines 3a–j to ethyl propiolate 4 gave cycloadducts 5a–h and 5′i and 5/5′j as single regioisomers. In terms of facial selectivity, cycloadducts 5a–h and 5′i were obtained as single diastereomers, whereas the reaction of dipole 3j was less selective and gave a mixture of 5j and 5′j in a ratio of 15:85. Stereoselectivity of copper(i) iodide-catalyzed cycloadditions of ethyl propiolate 4 to azomethine imines 3 was controlled by the stereodirecting phenyl group at position 5 and by the ortho-substituents at the 1′–Ar residue.
Combinatorial solution-phase cycloadditions of (1Z,4R*,5R*)-4-benzoylamino-5-phenylpyrazolidin-3-on-1-azomethine imines 3 to beta-keto esters 4 afforded a library of 26 bicyclic pyrazolidinones 5 in 6-89% yields and in 14-100% de. All products were isolated in >90% purity according to 1H NMR, and 25 of them were analytically pure. The structures of cycloadducts were confirmed by NMR and X-ray diffraction. Most of the products were isolated as mixtures of the major (1S*,2S*,3R*,5R*,6R*)-epimers 5 and the minor (1R*,2S*,3R*,5R*,6R*)-epimers 6. Epimerization of cycloadducts 5/6 at the anomeric position 1 in solution was confirmed by 1H NMR.
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