Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2021 Feb;193(2):560-576.
doi: 10.1007/s12010-020-03442-3. Epub 2020 Oct 12.

Immobilized Arabidopsis thaliana Hydroxynitrile Lyase-Catalyzed Retro-Henry Reaction in the Synthesis of (S)-β-Nitroalcohols

D H Sreenivasa Rao  1 , Kummari Shivani  1 , Santosh Kumar Padhi  2
Affiliations

Immobilized Arabidopsis thaliana Hydroxynitrile Lyase-Catalyzed Retro-Henry Reaction in the Synthesis of (S)-β-Nitroalcohols

D H Sreenivasa Rao et al. Appl Biochem Biotechnol. 2021 Feb.

Abstract

Enantiopure β-nitroalcohols are versatile intermediates used in the synthesis of important pharmaceuticals and chiral synthons. In this article, immobilized Arabidopsis thaliana HNL (AtHNL)-catalyzed preparation of (S)-β-nitroalcohols from their racemic mixtures via retro-Henry reaction was studied. AtHNL used in biocatalysis was immobilized by physical adsorption in inexpensive celite®545. Under optimized biocatalytic conditions, the total turnover number of the catalyst has improved 2.3-fold for (S)-2-nitro-1-phenylethanol (NPE) synthesis, than free enzyme catalysis. This study reported for the first time celite-AtHNL-catalyzed retro-Henry reaction at low pH. At pH 4.5 and 5.0, 62% ee and 41% conversion, and 97% ee and 42% conversion of (S)-NPE were obtained respectively, while the free enzyme inactivates at pH < 5.0. The increased catalytic efficiency and pH stability of the catalyst could be possibly due to increased stability of AtHNL by immobilization. A dozen of racemic β-nitroalcohols were converted into their corresponding (S)-β-nitroalcohols using this reaction; among them, eight were not tested earlier. The immobilized enzyme has showed broad substrate selectivity in the retro-Henry reaction, and products were obtained up to 98.5% ee.

Keywords: Biocatalysis; Hydroxynitrile lyase; Immobilization; Retro-Henry reaction; β-Nitroalcohols.

PubMed Disclaimer

References

    1. Milner, S. E., Moody, T. S., & Maguire, A. R. (2012). Biocatalytic approaches to the Henry (nitroaldol) reaction. European Journal of Organic Chemistry, 16(16), 3059–3067. https://doi.org/10.1002/ejoc.201101840 . - DOI
    1. Guo, Z. L., Deng, Y. Q., Zhong, S., & Lu, G. (2011). Enantioselective synthesis of (R)-salmeterol employing an asymmetric Henry reaction as the key step. Tetrahedron: Asymmetry, 22(13), 1395–1399. https://doi.org/10.1016/j.tetasy.2011.08.008 . - DOI
    1. Sasai, H., Itoh, N., Suzuki, T., & Shibasaki, M. (1993). Catalytic asymmetric nitroaldol reaction: an efficient synthesis of (S) propranolol using the lanthanum binaphthol complex. Tetrahedron Letters, 34(5), 855–858. https://doi.org/10.1016/0040-4039(93)89031-K . - DOI
    1. Sasai, H., Yamada, Y. M. A., & Takeyuki Suzuki, M. S. (1994). Synthesis of (S)-(-)-pindolol and [3’-13C]-(R)-(-)-pindolol utilizing a lanthanum-lithium-(R)-BINOL ((R)-LLB) catalyzed nitroaldol reaction. Tetrahedron, 50(43), 12313–12318. https://doi.org/10.1016/S0040-4039(99)00636-X . - DOI
    1. Ananthi, N., & Velmathi, S. (2013). Asymmetric Henry reaction catalysed by transition metal complexes: a short review. Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 52(1), 87–108.

MeSH terms

LinkOut - more resources