Dedicated to Professor Rugang Xie on the occasion of his 70th birthdayEnantiomerically enriched a-hydroxy-functionalized phosphonates and phosphonic acids have been widely employed to synthesize pharmaceutically and biologically active compounds. [1, 2] Catalytic asymmetric hydrophosphonylation by addition of an appropriate phosphorus nucleophile to the carbonyl bond can provide a very convenient route to the corresponding optically active a-hydroxy phosphonates, which is probably the most general and widely applied approach. [1b] Much effort has been directed towards the development of this important type of asymmetric reaction. Shibasaki and co-workers described the first highly enantioselective addition of aldehydes with dimethyl phosphite using a heterobimetallic multifunctional catalyst based on 1,1'-bi-2naphthol (binol). However, the catalytic system only gave rise to moderate enantioselectivities for aliphatic aldehydes. [3] A breakthrough was achieved with the C 1 -symmetric [Al-(salalen)] complex by Katsuki and co-workers (salalen = salen/salan hybrid; salen = N,N-bis(salicylidene)ethylene diamine; salan = N,N-bis(O-hydroxybenzyl)-1,2-diaminoethane). [4] Quite recently, Feng and co-workers presented another highly enantioselective example promoted by the tridentate Schiff base/Al III complexes. [5] However, among these most outstanding examples, relatively high catalyst loadings and/or extended reaction times were generally required to induce acceptable conversions. [3][4][5][6] Clearly, the development of more efficient and practical catalytic systems for a broad range of phosphites and aldehydes (both aromatic and aliphatic) is a highly challenging topic.The strategy of synergistic activation by two or more reactive centers constitutes a versatile approach for the development of high-performance asymmetric catalysis. [7,8] Recently, the concept of self-assembly by metal-organic coordination has been successfully employed to construct combinatorial chiral catalysts. [9,10] We wish to report the combination of the two concepts mentioned above to obtain a new type of bifunctional catalyst generated by the metalorganic self-assembly of substituted binols [3,11] and cinchona alkaloids [12] in combination with Ti(OiPr) 4 [13] for the asymmetric hydrophosphonylation of aldehydes. The chiral Lewis base moiety (cinchona alkaloid) in these self-assembled bifunctional catalysts spontaneously coordinates to the central metal of the chiral Lewis acidic moiety (binol-Ti complex) to form the metal-organic assemblies (Figure 1).In comparison with the conventional bifunctional catalysts in which Lewis acid/Lewis base (LALB) moieties are integrated into one molecule through covalent bonds, [6b, 8a-g] the highly modular nature of the catalyst systems would easily allow better matching of the chiral ligand, metal ion, and substrate, and thus facilitate the achievement of excellent catalytic performance (activity and enantioselectivity; Scheme 1).Preliminary experiments focused on varying the reaction parameters, such...