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Sustainable Aldehyde Oxidations in Continuous Flow Using in Situ-Generated Performic Acid

  • Michael Prieschl
    Michael Prieschl
    Center for Continuous Flow Synthesis and Processing (CCFLOW), Research Center Pharmaceutical Engineering GmbH (RCPE), Inffeldgasse 13, A-8010 Graz, Austria
    Institute of Chemistry, University of Graz, NAWI Graz, Heinrichstrasse 28, A-8010 Graz, Austria
  • Sándor B. Ötvös*
    Sándor B. Ötvös
    Center for Continuous Flow Synthesis and Processing (CCFLOW), Research Center Pharmaceutical Engineering GmbH (RCPE), Inffeldgasse 13, A-8010 Graz, Austria
    Institute of Chemistry, University of Graz, NAWI Graz, Heinrichstrasse 28, A-8010 Graz, Austria
    *S.B.Ö.: email, [email protected]
  • , and 
  • C. Oliver Kappe*
    C. Oliver Kappe
    Center for Continuous Flow Synthesis and Processing (CCFLOW), Research Center Pharmaceutical Engineering GmbH (RCPE), Inffeldgasse 13, A-8010 Graz, Austria
    Institute of Chemistry, University of Graz, NAWI Graz, Heinrichstrasse 28, A-8010 Graz, Austria
    *C.O.K.: email, [email protected]
Cite this: ACS Sustainable Chem. Eng. 2021, 9, 16, 5519–5525
Publication Date (Web):April 14, 2021
https://doi.org/10.1021/acssuschemeng.1c01668
Copyright © 2021 The Authors. Published by American Chemical Society

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    Abstract

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    The oxidation of aldehydes is one of the most prevalent methods for the synthesis of a diverse range of carboxylic acids. We herein present a performic acid generator and its application for aldehyde oxidations under continuous flow conditions. Low molecular weight performic acid, an environmentally benign and inexpensive oxidant, was readily formed in situ from formic acid and hydrogen peroxide. The safety hazards typically encountered when manipulating this potentially explosive reagent were eliminated, while at the same time a clean and efficient access to valuable carboxylic acids was ensured. By taking advantage of concentrated or even neat aldehyde streams, the amount of organic solvents utilized, and thus waste formation, was successfully minimized as demonstrated by E-factors in the range of 5–18. The process proved applicable for a wide range of aromatic as well as aliphatic aldehydes, while its synthetic utility and stability were corroborated by scale-out experiments leading to multigram-scale syntheses.

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    • Synthetic procedures, additional reaction data, compound characterization data, and NMR spectra(PDF)

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    Cited By

    This article is cited by 14 publications.

    1. Parth Naik, Jorge García-Lacuna, Patrick O’Neill, Marcus Baumann. Continuous Flow Oxidation of Alcohols Using TEMPO/NaOCl for the Selective and Scalable Synthesis of Aldehydes. Organic Process Research & Development 2024, 28 (5) , 1587-1596. https://doi.org/10.1021/acs.oprd.3c00237
    2. Aitor Maestro, Bence S. Nagy, Sándor B. Ötvös, C. Oliver Kappe. A Telescoped Continuous Flow Enantioselective Process for Accessing Intermediates of 1-Aryl-1,3-diols as Chiral Building Blocks. The Journal of Organic Chemistry 2023, 88 (21) , 15523-15529. https://doi.org/10.1021/acs.joc.3c02040
    3. Jun Xu, Xiaoguang Yue, Lei He, Jiabin Shen, Yani Ouyang, Chenfeng Liang, Wanmei Li. Photoinduced Protocol for Aerobic Oxidation of Aldehydes to Carboxylic Acids under Mild Conditions. ACS Sustainable Chemistry & Engineering 2022, 10 (43) , 14119-14125. https://doi.org/10.1021/acssuschemeng.1c06755
    4. Bo Wu, Xiue Jiang, Yalin Yang, Huiying Du, Xianrui Shi, Zhaoqian Li, Chonghua Pei. Continuous-Flow Oxidation of Amines Based on Nitrogen-Rich Heterocycles: A Facile and Sustainable Approach for Promising Nitro Derivatives. Organic Process Research & Development 2022, 26 (10) , 2823-2829. https://doi.org/10.1021/acs.oprd.2c00162
    5. Laurent Vanoye, Alain Favre-Réguillon. Mechanistic Insights into the Aerobic Oxidation of Aldehydes: Evidence of Multiple Reaction Pathways during the Liquid Phase Oxidation of 2-Ethylhexanal. Organic Process Research & Development 2022, 26 (2) , 335-346. https://doi.org/10.1021/acs.oprd.1c00399
    6. Bence S. Nagy, Patricia Llanes, Miquel A. Pericas, C. Oliver Kappe, Sándor B. Ötvös. Enantioselective Flow Synthesis of Rolipram Enabled by a Telescoped Asymmetric Conjugate Addition–Oxidative Aldehyde Esterification Sequence Using in Situ-Generated Persulfuric Acid as Oxidant. Organic Letters 2022, 24 (4) , 1066-1071. https://doi.org/10.1021/acs.orglett.1c04300
    7. Jiale Wu, Yuan Tao, Dang Cheng, Fener Chen. On-the-fly H2 degassing: Towards selective borohydride reduction of α, β-unsaturated esters to allylic alcohols in continuous microflow. Chemical Engineering Science 2023, 280 , 119044. https://doi.org/10.1016/j.ces.2023.119044
    8. Márk Molnár, C. Oliver Kappe, Sándor B. Ötvös. Merger of Visible Light‐Driven Chiral Organocatalysis and Continuous Flow Chemistry: An Accelerated and Scalable Access into Enantioselective α‐Alkylation of Aldehydes. Advanced Synthesis & Catalysis 2023, 365 (10) , 1660-1670. https://doi.org/10.1002/adsc.202300289
    9. Qi Zhang, Dongmao Yan, Lixia Li, Guoqiang Yin, Wei Wei, Wenxuan Sun, Shulong Li, Chuan Zhou, Dong Liu, Jingnan Zhao, Qingwei Meng. Continuous process for preparation of 2,3-dimethyl-4-methylsulfonylbromobenzene via oxidation by in situ formed peracetic acid. Chemical Engineering and Processing - Process Intensification 2023, 184 , 109295. https://doi.org/10.1016/j.cep.2023.109295
    10. Bence S. Nagy, Gang Fu, Christopher A. Hone, C. Oliver Kappe, Sándor B. Ötvös. Harnessing a Continuous‐Flow Persulfuric Acid Generator for Direct Oxidative Aldehyde Esterifications. ChemSusChem 2023, 16 (2) https://doi.org/10.1002/cssc.202201868
    11. Bence S. Nagy, C. Oliver Kappe, Sándor B. Ötvös. N ‐Hydroxyphthalimide Catalyzed Aerobic Oxidation of Aldehydes under Continuous Flow Conditions. Advanced Synthesis & Catalysis 2022, 364 (12) , 1998-2008. https://doi.org/10.1002/adsc.202200124
    12. Songbo Xu, Xiaomin Zhang, Wenjie Xiong, Ping Li, Wentao Ma, Xingbang Hu, Youting Wu. Aerobic oxidation of aldehydes to acids in water with cyclic (alkyl)(amino)carbene copper under mild conditions. Chemical Communications 2022, 58 (13) , 2132-2135. https://doi.org/10.1039/D1CC04812K
    13. Florian Sommer, David Cantillo, C. Oliver Kappe. A small footprint oxycodone generator based on continuous flow technology and real-time analytics. Journal of Flow Chemistry 2021, 11 (4) , 707-715. https://doi.org/10.1007/s41981-021-00193-y
    14. Sándor B. Ötvös, C. Oliver Kappe. Continuous flow asymmetric synthesis of chiral active pharmaceutical ingredients and their advanced intermediates. Green Chemistry 2021, 23 (17) , 6117-6138. https://doi.org/10.1039/D1GC01615F

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