Modular Assembly Of Novel Dna-based Catalysts

摘要

A novel modular strategy towards the assembly of DNA-based catalysts containing a covalently anchored metal complex is presented.rnHybrid catalysis has emerged as a powerful catalytic concept. In hybrid catalysis, a catalytically active transition metal complex is anchored to a biopolymer scaffold, e.g. a protein or a polynucleotide, and the second coordination sphere that is provided by the biopolymer imparts (enantio-)selectivity and, in some cases, increased efficiency to the reaction. Three general anchoring strategies can be distinguished: supramolecular, dative and covalent anchoring. The supramolecular and dative anchoring strategies have proven to be very successful; a wide variety of highly enantioselective reactions have been reported using this approach. In contrast, the enantioselectivities that have been reported to date when using the covalent anchoring strategy have been generally more modest. Arguably, one of the main reasons for this is that the optimization of these hybrid catalysts is much more laborious and time-consuming. Yet, a covalent anchoring strategy potentially has many advantages since it allows for precise positioning of the metal complex and, hence, control over the structure and geometry of the catalytic site. Here we present a novel modular strategy towards DNA-based catalysts containing a covalently anchored metal complex that allows for rapid optimization.