Synfacts 2017; 13(03): 0309
DOI: 10.1055/s-0036-1590002
Organo- and Biocatalysis
© Georg Thieme Verlag Stuttgart · New York

Nonnatural Reactivity of Cofactor-Dependent Enzymes upon Light Irradiation

Benjamin List
Grigory A. Shevchenko
Emmanuel MA. Greenberg NR. Oblinsky DG. Hyster TK. * Princeton University, USA
Accessing Non-Natural Reactivity by Irradiating Nicotinamide-Dependent Enzymes with Light.

Nature 2017;
540: 414-417
Further Information

Publication History

Publication Date:
15 February 2017 (online)



An asymmetric light-mediated reductive debromination of racemic α-bromolactones is reported by the Hyster group. The combination of a ketoreductase derived from either Lactobacillus kefiri (LKADH) or Ralstonia (RasADH), NADP+, and blue LED light furnished the desired lactones in high yields (≤91%) and good to excellent enantioselectivities (er ≤ 98:2).



A great challenge in biocatalysis is the discovery and development of novel reaction pathways and catalytic functions. The authors demonstrate that a nicotinamide-dependent keto­reductase can change its natural function from carbonyl reduction to that of a radical initiator and chiral source of hydrogen, simply by irradiation of the cofactor with light. This strategy leads to novel and selective radical-mediated reactions.