DNA-cellulose: an economical, fully recyclable and highly effective chiral biomaterial for asymmetric catalysis

Abstract

The challenge in DNA-based asymmetric catalysis is to perform a reaction in the vicinity of the helix by incorporating a small-molecule catalyst anchored to the DNA in a covalent, dative, or non-covalent yet stable fashion in order to ensure high levels of enantio-discrimination. Here, we report the first generation of a DNA-based catalyst bound to a cellulose matrix. The chiral biomaterial is commercially available, trivial to use, fully recyclable and produces high levels of enantioselectivity in various Cu(II)-catalyzed asymmetric reactions including Friedel-Crafts alkylations and Michael additions. A single-pass, continuous-flow process is also reported affording fast conversions and high enantioselectivities at low catalyst loadings thus offering a new benchmark in the field of DNA-based asymmetric catalysis.

The new breed of cutting-edge catalysts

“…The spiral grooves align the reactants so that they fuse with the desired chiral configuration. In 2015, Arseniyadis and Smietana reported a recyclable DNA-copper catalyst 13 that created the correct chiral products as reactants flowed past. With endless combinations of base pairs and metal ions, "there's a plethora of parameters that you can fine-tune", says Arseniyadis.…”

Coordination complexes and biomolecules: A wise wedding for catalysis upgrade

“…This would have fostered a rapid and rational improvement of key features. The use of solid-phase supported DNA was recently reported, allowing the development of such catalysis at synthetically relevant scale and enabling recycling of the catalyst [62,63].…”

Recent Advances in Continuous‐Flow Enantioselective Catalysis

“…Recently, a DNA‐based catalyst showed high enantioselectivity for Cu II ‐catalyzed asymmetric Friedel–Crafts alkylations and Michael additions. Arseniyadis and co‐workers developed a cheap and reusable Cu‐based cellulose‐supported double‐stranded calf thymus DNA (ct‐DNA) catalyst . This CS‐ct‐DNA‐Cu(dmbpy) biohybrid catalyst was used in the Friedel–Crafts alkylation of α,β‐unsaturated imidazole 123 to 5‐methoxyindole 124 under batch process first.…”