Ab ifunctional amine/squaramide catalyst promoted direct aldol addition of an hydantoin surrogatet op yridine 2-carbaldehyde N-oxides to afforda dducts bearing two vicinal tertiary/quaternary carbonsi nhigh diastereo-and enantioselectivity (d.r.u pt o> 20:1; ee up to 98 %) is reported. Acid hydrolysis of adducts followedby reduction of the N-oxideg roup yields enantiopure carbinol-tethered quater-nary hydantoin-azaarene conjugates with denselyf unctionalized skeletons. DFT studies of the potential energy surface (B3LYP/6-31 + G(d) + CPCM (dichloromethane)) of the reaction correlate the activity of differentc atalysts and support an intramolecular hydrogen-bond-assisted activationo ft he squaramide moiety in the transition state of the catalytic reaction.[a] J. Izquierdo, N. Demurget, Dr.A.L anda, Prof. M. Oiarbide,P rof. C. Palomo Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.