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Supramolecular Catalysis with Chiral Mono- and Bis-(Thio)Urea-Derivatives

Veronica Iuliano, Paolo Della Sala, Carmen Talotta, Margherita De Rosa, Carmine Gaeta, Placido Neri, Annunziata Soriente

Organics · pp. 32–45 · Published 26 Mar 2024

10.3390/org5020003

Abstract

Chiral mono- and bis-(thio)urea supramolecular organocatalysts were studied in the enantioselective vinylogous addition reaction of 2-trimethylsilyloxyfuran (TMSOF) to carbonylic compounds; the corresponding chiral γ-hydroxymethyl-butenolides are obtained in good yields and with high enantiomeric excesses. The catalyst structure, as well as the reaction conditions, strongly influence the efficiency of the reaction. The conformational features of mono(thio)urea catalysts 2 and 3 and bis(thio)urea catalysts 7 and 8 were investigated by DFT calculations along with the structure of their complexes with benzaldehyde. Natural Bond Orbital (NBO) and Non-Covalent Interaction (NCI) calculations provided useful information concerning the activating H-bonding interactions in the complexes.

Thio- Supramolecular chemistry Urea Catalysis Chemistry Supramolecular catalysis Combinatorial chemistry Organic chemistry

References (44)

  1. 1 Breslow, 1982, Artificial Enzymes [DOI]
  2. 2 McMillan, 2008, The advent and development of organocatalysis. The advent and development of organocatalysis [DOI]
  3. 3 Raynal, 2014, Supramolecular catalysis. Part 1: Non-covalent interactions as a tool for building and modifying homogeneous catalysts [DOI]
  4. 4 Purse, 2005, Functional cavitands: Chemical reactivity in structured environments [DOI]
  5. 5 Meeuwissen, 2010, Supramolecular catalysis beyond enzyme mimics [DOI]
  6. 6 Gambaro, 2020, Kinetic and Thermodynamic Modulation of Dynamic Imine Libraries Driven by the Hexameric Resorcinarene Capsule [DOI]
  7. 7 Lloyd, G., and Forgan, R.S. (2021). Monographs in Supramolecular Chemistry, The Royal Society of Chemistry.
  8. 8 Iuliano, 2023, Supramolecular control on reactivity and selectivity inside the confined space of H-bonded hexameric capsules [DOI]
  9. 9 Zecchina, A., Bordiga, S., and Groppo, E.E. (2011). From Selective Nanocatalysts and Nanoscience, Wiley-VCH Verlag GmbH & Co. KGaA. [DOI]
  10. 10 Catti, 2016, Advantages of Catalysis in Self-Assembled Molecular Capsules [DOI]
  11. 11 Hong, 2018, Self-Assembled Tetrahedral Hosts as Supramolecular Catalysts [DOI]
  12. 12 Ren, 2021, Development of Efficient Solid Chiral Catalysts with Designable Linkage for Asymmetric Transfer Hydrogenation of Quinoline Derivatives [DOI]
  13. 13 Wang, 2023, Electron-Deficient Cu Site Catalyzed Acetylene Hydrochlorination [DOI]
  14. 14 Zhang, Z., Zhang, H., Wang, B., Yue, Y., and Zhao, J. (2023). Migration: A Neglected Potential Contribution of HCl-Oxidized Au(0). Molecules, 28. [DOI]
  15. 15 Doyle, 2007, Small-Molecule H-Bond Donors in Asymmetric Catalysis [DOI]
  16. 16 Taylor, 2006, Asymmetric Catalysis by Chiral Hydrogen-Bond Donors [DOI]
  17. 17 Li, 2022, Selective Hydrogenation of 5-(Hydroxymethyl)Furfural to 5-Methylfurfural by Exploiting the Synergy between Steric Hindrance and Hydrogen Spillover [DOI]
  18. 18 Wang, 2021, Palladium-Catalyzed Enantioselective Linear Allylic Alkylation of Vinyl Benzoxazinanones: An Inner-Sphere Mechanism [DOI]
  19. 19 Cafeo, 2008, Efficient organocatalysis with a calix[4]pyrrole derivative [DOI]
  20. 20 Cafeo, 2009, Calixpyrrole Derivatives: “Multi Hydrogen Bond” Catalysts for γ-Butenolide Synthesis [DOI]
  21. 21 Citro, 2006, The first organocatalytic addition of 2-trimethylsilyloxyfuran to carbonyl compounds: Hydrogen-bond catalysis in γ-butenolides synthesis [DOI]
  22. 22 Smith, 2000, Novel Polyketide Metabolites from a Species of Marine Fungi [DOI]
  23. 23 Antane, 2006, Pulvinones as bacterial cell wall biosynthesis inhibitors [DOI]
  24. 24 Li, 2005, Structure and anti-HIV activity of micrandilactones B and C, new nortriterpenoids possessing a unique skeleton from Schisandra micrantha [DOI]
  25. 25 Yu, 2021, Construction of Enantioenriched γ,γ-Disubstituted Butenolides Enabled by Chiral Amine and Lewis Acid Cascade Cocatalysis [DOI]
  26. 26 Hug, J.J., Kjaerulff, L., Garcia, R., and Müller, R. (2022). New Deoxyenhygrolides from Plesiocystis pacifica Provide Insights into Butenolide Core Biosynthesis. Mar. Drugs, 20. [DOI]
  27. 27 Pelter, 1987, Synthetic routes to the piperolides, fadyenolides, epoxypiperolides, and related compounds [DOI]
  28. 28 Boukouvalas, 1995, An efficient total synthesis of the antibiotic patulin [DOI]
  29. 29 Brown, 2003, The First Enantioselective Organocatalytic Mukaiyama−Michael Reaction:  A Direct Method for the Synthesis of Enantioenriched γ-Butenolide Architecture [DOI]
  30. 30 Singh, 2010, Asymmetric Vinylogous Aldol Reaction of Silyloxy Furans with a Chiral Organic Salt [DOI]
  31. 31 Pansare, 2011, The Organocatalytic Vinylogous Aldol Reaction: Recent Advances [DOI]
  32. 32 Wang, 2005, Chiral Binaphthyl-Derived Amine-Thiourea Organocatalyst-Promoted Asymmetric Morita−Baylis−Hillman Reaction [DOI]
  33. 33 Wang, 2005, Organocatalytic Asymmetric Michael Addition of 2,4-Pentandione to Nitroolefins [DOI]
  34. 34 Fleming, 2006, Novel axially chiral bis-arylthiourea-based organocatalysts for asymmetric Friedel–Crafts type reactions [DOI]
  35. 35 Ollevier, 2008, Diastereoselective Mukaiyama Aldol Reaction of 2-(Trimethylsilyloxy)Furan Catalyzed by Bismuth Triflate [DOI]
  36. 36 Capobianco, 2023, Confused-Prism[5]arene: A Conformationally Adaptive Host by Stereoselective Opening of the 1,4-Bridged Naphthalene Flap
  37. 37 Zhu, 2012, Insights into the Dual Activation Mechanism Involving Bifunctional Cinchona Alkaloid Thiourea Organocatalysts: An NMR and DFT Study [DOI]
  38. 38 Jakab, 2012, (Thio)urea Organocatalyst Equilibrium Acidities in DMSO [DOI]
  39. 39 Weinhold, F., and Landis, C.R. (2003). Valency and Bonding: A Natural Bond Orbital Donor-Acceptor Perspective, Cambridge University Press. [1st ed.]. [DOI]
  40. 40 2005, Chiral Fluorescent Receptors Based on (R)-1,1′-Binaphthylene-2,2′-bisthiourea: Synthesis and Chiral Recognition [DOI]
  41. 41 Sohtome, 2004, Development of bis-thiourea-type organocatalyst for asymmetric Baylis–Hillman reaction [DOI]
  42. 42 Berkessel, 2006, Asymmetric Morita−Baylis−Hillman Reaction Catalyzed by Isophoronediamine-Derived Bis(thio)urea Organocatalysts [DOI]
  43. 43 Szlosek, 2000, Highly Enantioselective Aldol Reaction with 2-Trimethylsilyloxyfuran: The First Catalytic Asymmetric Autoinductive Aldol Reaction [DOI]
  44. 44 Ghosh, 2020, C–H⋯S interaction exhibits all the characteristics of conventional hydrogen bonds [DOI]

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