Controllable stereoinversion in DNA-catalyzed olefin cyclopropanation cofactor modification
The assembly of DNA with metal-complex cofactors can form promising biocatalysts for asymmetric reactions, although catalytic performance is typically limited by low enantioselectivities and stereo-control remains a challenge. Here, we engineer G-quadruplex-based DNA biocatalysts for an asymmetric c...
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| Published in: | Chemical science (Cambridge) Vol. 12; no. 22; pp. 7918 - 7923 |
|---|---|
| Main Authors: | , , , , , |
| Format: | Journal Article |
| Published: |
09-06-2021
|
| Online Access: | Get full text |
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| Summary: | The assembly of DNA with metal-complex cofactors can form promising biocatalysts for asymmetric reactions, although catalytic performance is typically limited by low enantioselectivities and stereo-control remains a challenge. Here, we engineer G-quadruplex-based DNA biocatalysts for an asymmetric cyclopropanation reaction, achieving enantiomeric excess (ee
trans
) values of up to +91% with controllable stereoinversion, where the enantioselectivity switches to −72% ee
trans
through modification of the Fe-porphyrin cofactor. Complementary circular dichroism, nuclear magnetic resonance, and fluorescence titration experiments show that the porphyrin ligand of the cofactor participates in the regulation of the catalytic enantioselectivity
via
a synergetic effect with DNA residues at the active site. These findings underline the important role of cofactor modification in DNA catalysis and thus pave the way for the rational engineering of DNA-based biocatalysts.
Cofactor modification in a DNA-catalyzed olefin cyclopropanation reaction enables controllable stereoinversion and achieves enantioselectivities of up to +91% and −72% ee
trans
. |
|---|---|
| Bibliography: | 10.1039/d1sc00755f Electronic supplementary information (ESI) available. See DOI |
| ISSN: | 2041-6520 2041-6539 |
| DOI: | 10.1039/d1sc00755f |