Pure and Applied Chemistry

Abstract: Inspired by the principle of DNA base-pairing, a new concept for the self-assembly of molecular catalysts is described herein. Thus, employing A-T analogous complementary hydrogen-bonding templates, self-assembly of monodentate to bidentate ligands in the coordination sphere of a transition-metal salt occurs to give defined self-assembly catalysts. This approach is intrinsically combinatorial and allows the facile generation of defined catalyst libraries through simple component mixing. From the study of these ligand libraries, excellent catalysts for linear-selective hydroformylation, asymmetric hydrogenation, and anti-Markovnikov hydration of terminal alkynes have emerged.