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Pepsin-Catalyzed Asymmetric Cross Aldol Reaction Promoted by Ionic Liquids and Deep Eutectic Solvents

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Abstract

Pepsin was found to catalyze asymmetric cross aldol reactions of aromatic and polycyclicaromatic aldehydes with cyclic ketones in ionic liquids and deep eutectic solvents for the first time. Pepsin exhibited high catalytic activity and excellent stereoselectivity in ionic liquids and deep eutectic solvents in the presence of moderate water. High yields of up to 93.1%, excellent enantioselectivities of up to 96% ee, and good diastereoselectivities of up to 5:95 dr were achieved.

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References

  1. Guarneri A, van Berkel WJ, Paul CE (2019) Alternative coenzymes for biocatalysis. Curr Opin Biotechnol 60:63–71

    Article  CAS  Google Scholar 

  2. Turner NJ, Kumar R (2018) Editorial overview: biocatalysis and biotransformation: the golden age of biocatalysis. Curr Opin Chem Biol 43:A1–A3

    Article  CAS  Google Scholar 

  3. Dwivedee BP, Soni S, Sharma M, Bhaumik J, Laha JK, Banerjee UC (2018) Promiscuity of lipase catalyzed reactions for organic synthesis: a recent update. ChemistrySelect 3(9):2441–2466

    Article  CAS  Google Scholar 

  4. He W-X, Xing X, Yang Z-J, Yu Y, Wang N, Yu X-Q (2019) Biocatalytic one-pot three-component synthesis of indoloquinolizines with high diastereoselectivity. Catal Lett 249(2):638–643

    Article  Google Scholar 

  5. Koszelewski D, Ostaszewski R (2019) Biocatalytic promiscuity of lipases in carbon-phosphorus bond formation. ChemCatChem 11(10):2554–2558

    Article  CAS  Google Scholar 

  6. Cai J-F, Guan Z, He Y-H (2011) The lipase-catalyzed asymmetric C-C Michael addition. J Mol Catal B: Enzym 68(3–4):240–244

    Article  CAS  Google Scholar 

  7. Rizzo PVS, Boarin LA, Freitas IOM, Gomes RS, Beatriz A, Rinaldi AW, Domingues NLC (2014) The study of biocatalyzed thio-Michael reaction: a greener and multi-gram protocol. Tetrahedron Lett 55(2):430–434

    Article  CAS  Google Scholar 

  8. Jiang L, Wang B, Li R-R, Shen S, Yu H-W, Ye L-D (2014) Catalytic promiscuity of Escherichia coli BioH esterase: application in the synthesis of 3,4-dihydropyran derivatives. Process Biochem 49(7):1135–1138

    Article  CAS  Google Scholar 

  9. Wu L-L, Xiang Y, Yang D-C, Guan Z, He Y-H (2016) Biocatalytic asymmetric Mannich reaction of ketimines using wheat germ lipase. Catal Sci Technol 6(11):3963–3970

    Article  CAS  Google Scholar 

  10. Eremeev NL, Zaitsev SY (2016) Porcine pancreatic lipase as a catalyst in organic synthesis. Mini-Rev Org Chem 13(1):78–85

    Article  CAS  Google Scholar 

  11. Xu F, Xu J, Hu YJ, Lin XF, Wu Q (2016) One-pot bienzymatic cascade combining decarboxylative aldol reaction and kinetic resolution to synthesize chiral β-hydroxy ketone derivatives. RSC Adv 6(80):76829–76837

    Article  CAS  Google Scholar 

  12. Li W, Liu DN, Geng X, Li ZQ, Gao RJ (2019) Real-time regulation of catalysis by remotecontrolled enzyme-conjugated gold nanorod composites for aldol reaction-based applications. Catal Sci Technol 9:2221–2230

    Article  CAS  Google Scholar 

  13. Tian X-M, Zhang S-Q, Zheng L-Y (2016) Enzyme-catalyzed henry reaction in choline chloride-based deep eutectic solvents. J Microbiol Biotechnol 26(1):80–88

    Article  CAS  Google Scholar 

  14. Foley M, Gavin DP, Deasy RE, Milner SE, Moody TS, Eccles KS, Lawrence SE, Maguire AR (2018) Dynamic kinetic resolution of 2-methyl-2-nitrocyclohexanol: combining the intramolecular nitroaldol (Henry) reaction & lipase catalysed resolution. Tetrahedron 74(13):1435–1443

    Article  CAS  Google Scholar 

  15. Ranganathan S, Gärtner T, Wiemann LO, Sieber V (2015) A one pot reaction cascade of in situ hydrogen peroxide production and lipase mediated in situ production of peracids for the epoxidation of monoterpenes. J Mol Catal B 114:72–76

    Article  CAS  Google Scholar 

  16. Branneby C, Carlqvist P, Magnusson A, Hult K, Brinck T, Berglund P (2003) Carbon-carbon bonds by hydrolytic enzymes. J Am Chem Soc 125(4):874–875

    Article  CAS  Google Scholar 

  17. He Y-H, Li H-H, Chen Y-L, Xue Y, Yuan Y, Guan Z (2012) Chymopapain-catalyzed direct asymmetric aldol reaction. Adv Synth Catal 354(4):712–719

    Article  CAS  Google Scholar 

  18. Chen X, Liu B-K, Kang H, Lin X-F (2011) A tandem Aldol condensation/dehydration co-catalyzed by acylase and N-heterocyclic compounds in organic media. J Mol Catal B: Enzym 68(1):71–76

    Article  CAS  Google Scholar 

  19. Li C, Feng X-W, Wang N, Zhou Y-J, Yu X-Q (2008) Biocatalytic promiscuity: the first lipase-catalysed asymmetric aldol reaction. Green Chem 10(6):616–618

    Article  CAS  Google Scholar 

  20. Carrea G, Ottolina G, Riva S (1995) Role of solvents in the control of enzyme selectivity in organic media. Trends Biotechnol 13(2):63–70

    Article  CAS  Google Scholar 

  21. Klibanov AM (2001) Improving enzymes by using them in organic solvents. Nature 409(6817):241–246

    Article  CAS  Google Scholar 

  22. Li H-H, He Y-H, Yuan Y, Guan Z (2011) Nuclease p1: a new biocatalyst for direct asymmetric aldol reaction under solvent-free conditions. Green Chem 13(1):185–189

    Article  CAS  Google Scholar 

  23. Xie Z-B, Wang N, Zhou L-H, Wan F, He T, Le Z-G, Yu XQ (2013) Lipase-catalyzed stereoselective cross-aldol reaction promoted by water. ChemCatChem 5(7):1935–1940

    Article  CAS  Google Scholar 

  24. Xie Z-B, Wang N, Jiang G-F, Yu X-Q (2013) Biocatalytic asymmetric aldol reaction in buffer solution. Tetrahedron Lett 54(8):945–948

    Article  CAS  Google Scholar 

  25. Ksenia SE, Valentine PA (2018) Ionic liquids in whole-cell biocatalysis: a compromise between toxicity and efficiency. Biophys Rev 10(3):881–900

    Article  Google Scholar 

  26. Zhang Y, Wang N, Xie Z-B, Zhou L-H, Yu X-Q (2014) Ionic liquid as a recyclable and efficient medium for lipase-catalyzed asymmetric cross aldol reaction. J Mol Catal B 110:100–110

    Article  CAS  Google Scholar 

  27. Abbott AP, Capper G, Davies DL, Munro HL, Rasheed RK, Tambyrajah V (2001) Preparation of novel, moisture-stable, Lewis-acidic ionic liquids containing quaternary ammonium salts with functional side chains. Chem Commun 19:2010–2011

    Article  Google Scholar 

  28. Smith L, Abbott AP, Ryder KS (2014) Deep eutectic solvents (DESs) and their applications. Chem Rev 114(21):11060–11082

    Article  CAS  Google Scholar 

  29. Zhang M, Liu Y-H, Shang Z-R, Hu H-C, Zhang Z-H (2017) Supported molybdenum on graphene oxide/Fe3O4: an efficient, magnetically separable catalyst for one-pot construction of spiro-oxindole dihydropyridines in deep eutectic solvent under microwave irradiation. Catal Commun 88:39–44

    Article  CAS  Google Scholar 

  30. Liu P, Hao J-W, Mo L-P, Zhang Z-H (2015) Recent advances in the application of deep eutectic solvents as sustainable media as well as catalysts in organic reactions. RSC Adv 5:48675–48704

    Article  CAS  Google Scholar 

  31. Gao G, Wang P, Liu P, Zhang W-H, Mo L-P, Zhang Z-H (2018) Deep Eutectic solvent catalyzed one-pot synthesis of 4,7-dihydro-1H-pyrazolo[3,4-b]pyridine-5-carbonitriles. Chin J Org Chem 38:846–854

    Article  CAS  Google Scholar 

  32. González-Martínez D, Gotor V, Gotor-Fernández V (2016) Application of deep eutectic solvents in promiscuous lipase catalysed aldol reactions. Eur J Org Chem 8:1513–1519

    Article  Google Scholar 

  33. Choi YS, Yoo YJ (2012) A hydrophilic and hydrophobic organic solvent mixture enhances enzyme stability in organic media. Biotechnol Lett 34(6):1131–1135

    Article  CAS  Google Scholar 

  34. Yang Z, Pan W (2005) Ionic liquids: Green solvents for nonaqueous biocatalysis. Enzyme Microb Technol 37(1):19–28

    Article  CAS  Google Scholar 

  35. Zhang W, Zhao Z-Y, Wang Z, Guo C, Wang C-Y, Zhao R, Wang L (2017) Lipase-catalyzed synthesis of Indolyl 4H-chromenes via a multicomponent reaction in ionic liquid. Catalysts 7:185–194

    Article  Google Scholar 

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Acknowledgements

We gratefully acknowledge the Natural Science Foundation of Guangdong Province (Grant No. 2018A030307022), Special Innovation Projects of Common Universities in Guangdong Province (Grant No. 2018KTSCX126).

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Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Key Laboratory of Clean Energy Materials Chemistry of Guangdong Higher Education Institutes, LingNan Normal University, Zhanjiang, 524048, China

    Yun Wang, Xin-Yi Chen, Xin-Yi Liang, Zhi-Hui Liang, Hong Cheng, Xiang Li & Li-Ling Li

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  1. Yun Wang
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  2. Xin-Yi Chen
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  4. Zhi-Hui Liang
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Correspondence to Yun Wang.

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Wang, Y., Chen, XY., Liang, XY. et al. Pepsin-Catalyzed Asymmetric Cross Aldol Reaction Promoted by Ionic Liquids and Deep Eutectic Solvents. Catal Lett 150, 2549–2557 (2020). https://doi.org/10.1007/s10562-020-03176-1

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  • DOI: https://doi.org/10.1007/s10562-020-03176-1

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