González‐Rodríguez, Jorge;
González‐Granda, Sergio;
Kumar, Hirdesh;
Alvizo, Oscar;
Escot, Lorena;
Hailes, Helen C;
Gotor‐Fernández, Vicente;
(2024)
BioLindlar Catalyst: Ene‐Reductase‐Promoted Selective Bioreduction of Cyanoalkynes to Give (Z)‐Cyanoalkenes.
Angewandte Chemie
, 136
(39)
, Article e202410283. 10.1002/ange.202410283.
Preview |
PDF
Ivan et al Angew Chem Int Ed-2024.pdf - Published Version Download (2MB) | Preview |
Abstract
The direct synthesis of alkenes from alkynes usually requires the use of transition-metal catalysts. Unfortunately, efficient biocatalytic alternatives for this transformation have yet to be discovered. Herein, the selective bioreduction of electron-deficient alkynes to alkenes catalysed by ene-reductases (EREDs) is described. Alkynes bearing ketone, aldehyde, ester, and nitrile moieties have been effectively reduced with excellent conversions and stereoselectivities, observing clear trends for the E/Z ratios depending on the nature of the electron-withdrawing group. In the case of cyanoalkynes, (Z)-alkenes were obtained as the major product, and the reaction scope was expanded to a wide variety of aromatic substrates (up to >99 % conversion, and Z/E stereoselectivities of up to >99/1). Other alkynes containing aldehyde, ketone, or ester functionalities also proved to be excellent substrates, and interestingly gave the corresponding (E)-alkenes. Preparative biotransformations were performed on a 0.4 mmol scale, producing the desired (Z)-cyanoalkenes with good to excellent isolated yields (63–97 %). This novel reactivity has been rationalised through molecular docking by predicting the binding poses of key molecules in the ERED-pu-0006 active site
| Type: | Article |
|---|---|
| Title: | BioLindlar Catalyst: Ene‐Reductase‐Promoted Selective Bioreduction of Cyanoalkynes to Give (Z)‐Cyanoalkenes |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1002/ange.202410283 |
| Publisher version: | https://doi.org/10.1002/ange.202410283 |
| Language: | English |
| Additional information: | © 2024 The Author(s). This is an open access article under the terms of the Creative Commons Attribution-NonCommercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes. |
| Keywords: | alkynes, biocatalysis, cyanoalkenes, ene-reductases, semireduction |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry |
| URI: | https://discovery.ucl.ac.uk/id/eprint/10197392 |
Archive Staff Only
 |
View Item |
