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Ayhan MM, Karoui H, Hardy M, et al. Comprehensive Synthesis of Monohydroxy-Cucurbit[n]urils (n = 5, 6, 7, 8): High Purity and High Conversions. J Am Chem Soc. 2015;137(32):10238-45doi: 10.1021/jacs.5b04553.
Ayhan, M. M., Karoui, H., Hardy, M., Rockenbauer, A., Charles, L., Rosas, R., Udachin, K., Tordo, P., Bardelang, D., & Ouari, O. (2015). Comprehensive Synthesis of Monohydroxy-Cucurbit[n]urils (n = 5, 6, 7, 8): High Purity and High Conversions. Journal of the American Chemical Society, 137(32), 10238-45. https://doi.org/10.1021/jacs.5b04553
Ayhan, Mehmet M, et al. "Comprehensive Synthesis of Monohydroxy-Cucurbit[n]urils (n = 5, 6, 7, 8): High Purity and High Conversions." Journal of the American Chemical Society vol. 137,32 (2015): 10238-45. doi: https://doi.org/10.1021/jacs.5b04553
Ayhan MM, Karoui H, Hardy M, Rockenbauer A, Charles L, Rosas R, Udachin K, Tordo P, Bardelang D, Ouari O. Comprehensive Synthesis of Monohydroxy-Cucurbit[n]urils (n = 5, 6, 7, 8): High Purity and High Conversions. J Am Chem Soc. 2015 Aug 19;137(32):10238-45. doi: 10.1021/jacs.5b04553. Epub 2015 Aug 05. PMID: 26197228.
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J Am Chem Soc. 2015 Aug 19;137(32):10238-45. doi: 10.1021/jacs.5b04553. Epub 2015 Aug 05.

Comprehensive Synthesis of Monohydroxy-Cucurbit[n]urils (n = 5, 6, 7, 8): High Purity and High Conversions.

Journal of the American Chemical Society

Mehmet M Ayhan, Hakim Karoui, Micaël Hardy, Antal Rockenbauer, Laurence Charles, Roselyne Rosas, Konstantin Udachin, Paul Tordo, David Bardelang, Olivier Ouari

Affiliations

  1. †Aix-Marseille Université, CNRS, Institut de Chimie Radicalaire, UMR 7273, 13397 Marseille, France.
  2. ‡Department of Chemistry, Gebze Technical University, P.K.:141, 41400 Gebze, Kocaeli, Turkey.
  3. § Institute of Materials and Environmental Chemistry, Hungarian Academy of Sciences, Department of Physics, Budapest University of Technology and Economics, Budafoki ut 8, 1111 Budapest, Hungary.
  4. ?Aix-Marseille Université, CNRS, Spectropole, FR 1739, 13013 Marseille, France.
  5. ?National Research Council Canada, 100 Sussex Drive, Ottawa, ON K1A 0R6, Canada.

PMID: 26197228 DOI: 10.1021/jacs.5b04553

Abstract

We describe a photochemical method to introduce a single alcohol function directly on cucurbit[n]urils (n = 5, 6, 7, 8) with conversions of the order 95-100% using hydrogen peroxide and UV light. The reaction was easily scaled up to 1 g for CB[6] and CB[7]. Spin trapping of cucurbituril radicals combined with MS experiments allowed us to get insights about the reaction mechanism and characterize CB[5], CB[6], CB[7], and CB[8] monofunctional compounds. Experiments involving (18)O isotopically labeled water indicated that the mechanism was complex and showed signs of both radical and ionic intermediates. DFT calculations allowed estimating the Bond Dissociation Energies (BDEs) of each hydrogen atom type in the CB series, providing an explanation of the higher reactivity of the "equatorial" C-H position of CB[n] compounds. These results also showed that, for CB[8], direct functionalization on the cucurbituril skeleton is more difficult because one of the methylene hydrogen atoms (Hb) has its BDE lowering within the series and coming close to that of Hc, thus opening the way to other types of free radicals generated on the CB[8] skeleton leading to several side products. Yet CB[5]-(OH)1 and CB[8]-(OH)1, the first CB[8] derivative, were obtained in excellent yields thanks to the soft method presented here.

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