The present invention pertains generally to compositions comprising organocatalysts that facilitate stereo-selective reactions and the method of their synthesis and use. Particularly, the invention relates to metal-free organocatalysts for facilitation of stereo-selective reactions, and the method of their synthesis and use. These compounds have the structure of the Formulas (I) and (II). Where X is independently selected from CH.sub.2, N--R.sup.a, O, S or C.dbd.O; Y is CH.sub.2, N--R.sup.a, O, S or C.dbd.O, with the proviso that at least one of X or Y is CH.sub.2, and preferably both of X and Y are CH.sub.2; R.sup.a is H, an optionally substituted C.sub.1-C.sub.12 alkyl, preferably an optionally substituted C.sub.1-C.sub.6alkyl including a C.sub.3-C.sub.6 cyclic alkyl group, or an optionally substituted aryl group, preferably an optionally substituted phenyl group; R.sup.b is H, an optionally substituted C.sub.1-C.sub.12 alkyl, preferably an optionally substituted C.sub.1-C.sub.6 acyclic or a a C.sub.3-C.sub.6 cyclic alkyl group, CIIO, N(Me)O, CO(S)R.sup.a or the group of Formula (III). Where R.sup.c and R.sup.d are each independently H, F, Cl, an optionally substituted C.sub.1-C.sub.20 alkyl, preferably an optionally substituted C.sub.1-C.sub.12 alkyl, more preferably a C.sub.1-C.sub.6 alkyl, and an optionally substituted aryl group, or together R.sup.c and R.sup.d form an optionally substituted carbocyclic or optionally substituted heterocyclic ring; R.sup.1 is OH, OR, NR'R'', NHC(.dbd.O)R, NHSO.sub.2R; R.sup.2 is H, F, Cl, an optionally substituted C.sub.1-C.sub.20 alkyl, preferably an optionally substituted C.sub.1C.sub.6 alkyl, an optionally substituted aryl group or a .dbd.O group (which establishes a carbonyl group with the carbon to which .dbd.O is attached; R.sup.3 is H, OH, F, Cl, Br, I, Cl, an optionally substituted C.sub.1-C.sub.20 alkyl, alkenyl or alkynyl ("hydrocarbyl") group, preferably an optionally substituted C.sub.1-C.sub.6 alkyl, or an optionally substituted aryl, such that the carbon to which R.sup.3 is attached has an R or S configuration; R is II, an optionally substituted C.sub.1-C.sub.20 alkyl, preferably an optionally substituted C.sub.1-C.sub.6 alkyl, or an optionally substituted aryl group, R' and R'' are each independently H, an optionally substituted C.sub.1-C.sub.20 alkyl group, preferably an optionally substituted C.sub.1-C.sub.6 alkyl, or an optionally substituted aryl group; or together R' and R'' form an optionally substituted heterocyclic, preferably a 4 to 7 membered optionally substituted heterocyclic group or an optionally substituted heteroaryl ring with the nitrogen to which R' and R'' are attached; and wherein said compound is free from a metal catalyst.