Study On Asymmetric Dearomation [3+2] Cycloaddition Reaction Of Aminocyclopropane With Benzoazole Compounds

Azole-derived is one kind of important nitrogen-containing aromatic heterocyclic compounds,which always exists as the core structure of natural and unnatural compounds.It has muitiple biological activities such as antibacterial,antifungal,anti-malaria,anti-parasite,anti-cancer and so on.They are key intermediates in organic synthesis.While the basic skeleton of non-aromatic pyrrole generally exists in bioactive natural products and their analogs.Therefore,it is of great significance to use aromatic heterocyclic compounds to construct a heterocyclic compound containing a complex chiral non-aromatic pyrrole structure.Herein,we report an enantioselective dearomative[3+2]cycloaddition reaction of benzazoles with aminocyclopropanes.In the presence of a copper complex,derived from Cu?OTf?₂ and bisoxazoline,a series of hydropyrrolo-benzazole derivatives containing a quaternary stereogenic center were obtained in high yields?up to 99%yield?with excellent enantioselectivity?up to 99%ee?.With the same catalytic system,2-amino cyclopropane-1,1-dicarboxylates with high enantiomeric purity?up to 98%ee?could also be obtained by an efficient kinetic resolution.The dearomatization products of the configuration.Benzothiazine and 1,5-benzothiazepine compounds were obtained by further derivatization of the product.We have performed data characterization on all the target compounds that have not been reported in the literature and are completely correct.The single crystal diffraction experiment was performed on some of the compounds to determine the structures of the compounds and the absolute structures of the chiral compounds.