Institute of Technical Chemistry, Department of Chemistry and Physics, Freiberg University of Mining and Technology, 09596, Freiberg, Germany.
Org Biomol Chem. 2011 Oct 26;9(22):7941-50. doi: 10.1039/c1ob06064c. Epub 2011 Oct 11.
In the field of industrial biocatalysis, formate dehydrogenase (FDH) is well established, in particular for its broad application in cofactor regeneration. Further applications have been limited by the enzyme's narrow range of substrates. These restrictions have been overcome now by the finding, that the enzyme is capable of selectively cleaving formic acid esters to the respective alcohol. Five homologous alkyl formates and phenyl formate as an aromatic ester were converted quantitatively by FDH from Candida boidinii in a batch reaction within 3 to 5 h. The substrates were turned irreversibly into carbon dioxide and the respective alcohol through hydride abstraction from the formyl group with full conversion. The mechanism shows parallels to hydrolysis reactions of the A(AC)1-type. K(M)-values and reactions rates of the tested formic acid esters display a tendency to higher conversion rates with increasing chain length. FDH emerged to be a superior deformylation catalyst compared to hydrolases as well as classical catalysts, as was shown by the selective deformylation of 1-acetoxy-4-formoxy butane (92%) and 1,3-bis(3-formoxypropyl)tetramethyldisiloxane. In particular its capability to distinguish between formic acid esters and non-formic acid esters renders the method particularly suitable for protective group chemistry. Furthermore the completeness of deformylation allows for converting substrates highly incompatible with aqueous media like siloxanes within a few hours.
在工业生物催化领域，甲酸脱氢酶（FDH）已经得到了广泛的应用，特别是在辅酶再生方面。然而，由于其底物范围狭窄，其进一步的应用受到了限制。现在，人们发现该酶能够选择性地将甲酸酯裂解为相应的醇，从而克服了这些限制。五种同源的烷基甲酸酯和苯甲酸盐作为芳香酯，在 Candida boidinii 的分批反应中，FDH 在 3 到 5 小时内可定量转化。底物通过从甲酰基中夺取氢原子不可逆地转化为二氧化碳和相应的醇，转化率达到 100%。该机制与 A(AC)1 型水解反应相似。测试的甲酸酯的 K(M)值和反应速率显示出随着链长的增加转化率有升高的趋势。FDH 作为一种优于水解酶和经典催化剂的脱甲酰基催化剂，通过选择性地脱甲酰基 1-乙酰氧基-4-甲氧基丁烷（92%）和 1,3-双（3-甲氧基丙基）四甲基二硅氧烷得到了证明。特别是它能够区分甲酸酯和非甲酸酯的能力，使得该方法特别适用于保护基化学。此外，脱甲酰基的完全性允许在几小时内将与水相不兼容的底物（如硅氧烷）转化。
