Biocatalysis and Enzyme Engineering Laboratory, Department of Biochemistry, School of Life Sciences, University of Hyderabad, Hyderabad, 500 046, India.
Chembiochem. 2024 Nov 4;25(21):e202400618. doi: 10.1002/cbic.202400618. Epub 2024 Sep 12.
A single enzyme, Baliospermum montanum hydroxynitrile lyase (BmHNL), without alteration, enabled bidirectional catalysis in enantiocomplementary synthesis of chiral β-nitroalcohols. BmHNL catalyzed promiscuous Henry (24 examples) and retro-Henry reaction (22 examples) provided up to >99 % and 50 % conversion to (S)- and (R)-β-nitroalcohols respectively, while both cases displayed up to >99 % ee. The broad substrate scope and high stereoselectivity of BmHNL represents its synthetic applications in sustainable production of diverse chiral β-nitroalcohols. Kinetic parameters of BmHNL was determined for Henry and retro-Henry reaction, which reveals poor catalytic efficiency for both the promiscuous transformations, however, the former has better efficiency than the latter. Practical applicability of the biocatalyst and transformation was illustrated by preparative scale synthesis of chiral intermediates of (S)-Tembamide, and (S)-Micanozole.
一种单一的酶，即巴厘岛熊果酸羟腈裂解酶（BmHNL），未经修饰，就能够在对映体互补合成手性β-硝基醇的过程中实现双向催化。BmHNL 催化混杂的 Henry（24 个实例）和反 Henry 反应（22 个实例），分别提供了高达>99%和 50%的转化率，得到（S）-和（R）-β-硝基醇，而两种情况下的对映体过量值都高达>99%。BmHNL 的广泛底物范围和高立体选择性代表了它在手性β-硝基醇的可持续生产中的合成应用。BmHNL 的动力学参数已确定用于 Henry 和反 Henry 反应，这表明两种混杂转化的催化效率都很差，但前者的效率优于后者。通过（S）-Tembamide 和（S）-Micanozole 的手性中间体的制备规模合成，说明了该生物催化剂和转化的实际适用性。
