The origin of enantioselectivity for intramolecular Friedel-Crafts reaction catalyzed by supramolecular Cu/DNA catalyst complex

•We investigated computationally of intramolecular Friedel-Crafts reaction.•This is the enantioselective reaction catalyzed by supramolecular Cu/DNA.•S-product selectivity is caused by higher binding energy of pro-S conformation.•The pro-S conformation is structurally closer to the C3-C2′ bond formation TS.

The present theoretical investigation aims at understanding the origin of enantioselectivity of intramolecular Friedel-Crafts reaction, catalyzed by supramolecular Cu/DNA catalyst. 28 Conformations of the supramolecular L-Cu(II)-R/d(CAAAAATTTTTG)2 complex were thoroughly modeled to estimate their stability and structural features depending on the metal complex conformation and its intercalation position. The preferred formation of S-product can be rationalized by the higher binding energy of pro-S conformations to DNA. Pro-S conformations are structurally closer to the expected C3-C2′ bond formation TS and usually not deeply buried into DNA, which would facilitate TS formation by decreasing the energy for conformational changes.

Graphical abstractDownload high-res image (168KB)Download full-size image