Polysaccharides as Sustainable Supports for Selective Organic Synthesis

Cellulose/Chitin/Chitosan are the most abundant polysaccharides on Earth. These homochiral polymers are essential for life as we know it. Cellulose is the main building block of trees and plants an important renewable resource for fabrication of every day products (e.g. dipers, pharmaceuticals, drug delivery, packaging, construction material, paper) for betterment of everyday life and human health. In the case of Chitin/Chitosan, it is the main structural component of arthropod exoskeleton and Fungi cell walls. The green and sustainable functionalization of these heterogeneous polysaccharides is important for the development of advanced sustainable materials.1,2 Another application for polysaccharide functionalization is to bind metal salts and metal-nano nanoparticles to them. Next, the resulting materials can be used as heterogeneous catalysts for green organic chemistry.1,2 In most cases, they were used for mediating cross-couplings reactions such as Heck and Suzuki. Together with Bäckvall’s research group we have taken this intrinsic ability of heterogeneous polysaccharides such as cellulose and chitosan to a new level and used them for chemo-, regio-, diastereo- and enantio-selective organic synthesis of complex molecules, natural products and pharmaceuticals.3-10

  1.  Córdova, A.; Afewerki, S.; Alimohammadzadeh, R.;  Sanhueza, I.; Tai, C.-W.; Osong, S.; Engstrand, P.; Ibrahem, I. A sustainable strategy for production and functionalization of nanocelluloses.  Pure Appl. Chem. 2019, 91, 865. 
  2. Afewerki, S.; Alimohammadzadeh, R.; Osong, S. H.; Tai, C.-W., Engstrand, P.;  Córdova, A. Sustainable design for the direct fabrication and highly versatile functionalization of nanocellulose. Global Challenges2017, 1, 1700045.
  3. Deiana, L.; Badali, E.; Rafi, A. A.; Tai, C.-W.; Bäckvall, J.-E.; Córdova, A. Cellulose-Based Heterogeneous Gold-Catalyzed Cycloisomerization Reactions of Alkynoic Acids and Allenynamides. ACS Catalysis 2023, 13, 10418–10424
  4. Wu, H.; Zheng, Z.; Zhang, K.; Kajanus, J.;  Johansson,M. J.; Córdova, A.; Bäckvall, J.-E. Heterogeneous Copper-Catalyzed Cross-Coupling for Sustainable Synthesis of 1,3-Di- and Tri-Substituted Chiral Allenes. Angew. Chem. Int. Ed. 2023, 62, e202314512
  5. Deiana, L.;  Rafi, A. A.; Tai, C.-W.; Bäckvall, J.-E.; Córdova, A. Artificial Arthropod Exoskeletons/Fungi Cell Walls as Sustainable Heterogeneous Multi-Catalytic Systems for Asymmetric Synthesis. ChemCatChem 2023, e202300250.
  6. Naidu, V. R.; Rafi, A.A.; Tai, C.-W.; Bäckvall, J.-E.; Córdova, A. Regio- and Stereoselective C-B Bond Formation via Heterogeneous Palladium-Catalyzed Hydroboration of Enallenes. Chem. Eur. J. 2023, 29, e202203950
  7. Deiana, L.; Rafi, A. A.; Bäckvall, J.-E.; Córdova, A.  Subtilisin integrated artificial plant cell walls as heterogeneous catalysts for asymmetric synthesis of (S)-amides. RSC Advances 2023, 13, 19975-19980
  8. Zheng, Z.; Deiana, L.; Posevins, D.; Rafi, A. A.; Zhang,K.; Johansson, M. J.; Tai,C.-W.; Córdova, A.; Bäckvall, J.-E. Efficient Heterogeneous Copper-Catalyzed Alder-Ene Reactions of Allenynamides to Pyrrolines. ACS Cat. 2022, 17, 1791.
  9. Deiana, L.; Rafi, A. A.; Naidu, V. R.; Tai, C.-W.; Bäckvall, J.-E.; Córdova, A. Artificial plant cell walls as multi-catalysts systems for enzymatic cooperative asymmetric catalysis in non-aqueous media. Chem. Commun. 2021, 57, 8814.  
  10. Li, M.-B.;  Yang, Y.; Rafi, A. A.; Oschmann, M.; Svensson Grape, E.; Inge, A. K.; Córdova, A.; Bäckvall, J.-E. Silver Triggering Activity of Heterogeneous Palladium Catalyst in Oxidative Carbonylation Reactions, Angew. Chem. Int. Ed. 2020, 59, 10391. https://doi.org/10.1002/anie.202001809