The 1,3-dipolar cycloaddition has been established as a reliable and powerful tool for the synthesis of heterocyclic compounds from simple starting materials. [1] In particular, the catalytic asymmetric 1,3-dipolar [3+2] cycloaddition of azomethine ylides with electron-deficient alkenes for the enantioselective preparation of structurally diverse pyrrolidines is probably one of the most studied asymmetric 1,3-dipolar cycloaddition reactions (Scheme 1 a), [2,3] and considerable progress has been made since the pioneering contributions from the research groups of Jørgensen [4] and Zhang.[5]However, in the past decade, most studies on the cycloaddition chemistry of azomethine ylides have been focused on the development of chiral catalysts for asymmetric [3+2] cycloaddition with electron-deficient alkenes as the reaction partner; other types of cycloaddition reactions (e.g., [3+3] or [3+4] cycloaddition) with azomethine ylides as one of the reaction partners have received little attention. Only recently, a novel cycloaddition reaction, the catalytic enantioselective [6+3] cycloaddition of azomethine ylides with fulvene to provide stereochemically rich piperidine derivatives, was developed independently by the research groups of Waldmann [6] and Wang [7] (Scheme 1 b). At present, the development of new and efficient catalytic enantioselective higherorder cycloaddition reactions to access chiral six-and sevenmembered rings and even larger heterocycles constitutes an important challenge. It was recently demonstrated that the zwitterion (which could be considered as a dipole) formed by the conjugate addition of a phosphine to an allenoate reacted with another kind of dipole in the form of azomethine imines in [8] Inspired by this study, we conceived that a metalcatalyzed asymmetric cycloaddition of a dipole with a dipole might be feasible. Such a reaction has never been explored in the cycloaddition chemistry of azomethine ylides. We envisaged that azomethine imines, which have been used extensively as 1,3-dipoles in various metal-catalyzed and organocatalytic cycloaddition reactions, [9] might serve as a threeatom synthon in a metal-catalyzed cycloaddition of azomethine ylides and undergo [3+3] cycloaddition to give biologically important hexahydro-8H-pyrazolo[1,2-a][1,2,4]triazin-8-one derivatives (Scheme 1 c).[10] Herein, we report the first asymmetric [3+3] cycloaddition of azomethine ylides with azomethine imines under the catalysis of a copper complex with a chiral ferrocenyl P,N ligand to provide 8-oxohexahydro-6H-pyrazolo[1,2-a][1,2,4]triazine-3-carboxylate derivatives with high diastereo-and enantioselectivities (Scheme 1 c).Both azomethine ylides and azomethine imines are versatile 1,3-dipoles and can be prepared readily from aldehydes. We began the study by examining the reaction between the azomethine ylide precursor 1 a and the azomethine imine 2 a (