8D4W

Asymmetric ene-reduction of alpha,beta-unsaturated compounds using MSMEG_2850

8D4W の概要

• エントリーDOI: 10.2210/pdb8d4w/pdb
• 分子名称: Cell entry (Mce) related family protein, GLYCEROL, DI(HYDROXYETHYL)ETHER, ... (4 entities in total)
• 機能のキーワード: f420, fdor, oxidoreductase
• 由来する生物種: Mycolicibacterium smegmatis
• タンパク質・核酸の鎖数: 1
• 化学式量合計: 15844.89

構造登録者

Kang, S.W.,Frkic, R.L.,Jackson, C. (登録日: 2022-06-02, 公開日: 2023-01-25, 最終更新日: 2023-10-25)

主引用文献

Kang, S.W.,Antoney, J.,Frkic, R.L.,Lupton, D.W.,Speight, R.,Scott, C.,Jackson, C.J.
Asymmetric Ene-Reduction of alpha , beta-Unsaturated Compounds by F 420 -Dependent Oxidoreductases A Enzymes from Mycobacterium smegmatis .
Biochemistry, 62:873-891, 2023

PubMed Abstract: The stereoselective reduction of alkenes conjugated to electron-withdrawing groups by ene-reductases has been extensively applied to the commercial preparation of fine chemicals. Although several different enzyme families are known to possess ene-reductase activity, the old yellow enzyme (OYE) family has been the most thoroughly investigated. Recently, it was shown that a subset of ene-reductases belonging to the flavin/deazaflavin oxidoreductase (FDOR) superfamily exhibit enantioselectivity that is generally complementary to that seen in the OYE family. These enzymes belong to one of several FDOR subgroups that use the unusual deazaflavin cofactor F. Here, we explore several enzymes of the FDOR-A subgroup, characterizing their substrate range and enantioselectivity with 20 different compounds, identifying enzymes (MSMEG_2027 and MSMEG_2850) that could reduce a wide range of compounds stereoselectively. For example, MSMEG_2027 catalyzed the complete conversion of both isomers of citral to ()-citronellal with 99% ee, while MSMEG_2850 catalyzed complete conversion of ketoisophorone to ()-levodione with 99% ee. Protein crystallography combined with computational docking has allowed the observed stereoselectivity to be mechanistically rationalized for two enzymes. These findings add further support for the FDOR and OYE families of ene-reductases displaying general stereocomplementarity to each other and highlight their potential value in asymmetric ene-reduction.

PubMed: 36637210
DOI: 10.1021/acs.biochem.2c00557

実験手法

X-RAY DIFFRACTION (1.35 Å)