Chiral cooperative catalysis enabling simultaneous activation of both an electrophile and a nucleophile has emerged as a powerful strategy in catalytic asymmetric synthesis. [1] In our laboratory, a series of novel hydrogen-bond functionalized salen-transition metal catalysts have been developed to facilitate bimetallic or bifunctional activation of both reaction partners (Figure 1). For example, a self-assembling dinuclear Co(II)-salen catalyst featuring the pyridone/aminopyridine H-bonding pair results in significant rate acceleration as well as excellent enantioselectivity in nitro-aldol reaction.[2] Bis-urea functionalized salen-Co(III) complexes exhibited significant rate acceleration in hydrolytic kinetic resolution of epoxides even at low catalyst loading (0.05 mol%).[3] The bis-urea salen-Co(III) complexes are also excellent catalysts for anti-selective asymmetric Henry reaction where broad substrate scope, good yield, excellent enantio- and diastereoselectivity were observed.[4] Recently, novel polyether-functionalized-salen Ni catalysts have been developed for the enantioselective direct alkynylation of trifluoromethyl ketones, affording enantioenriched propargyl alcohol products in high yields and enantioselectivities.[5] The current methodology is operationally simple and allow for the substoichiometric use of base. Ligand synthesis, catalyst/reaction optimization, substrate scope study results will be discussed in detail in the presentation.