Dissecting the Role of the Sergeants in Supramolecular Helical Catalysts: From Chain Capping to Intercalation.
helical catalyst
sergeants-and-soldiers effect
supramolecular catalysis
supramolecular chirality
supramolecular copolymerisation
Journal
Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543
Informations de publication
Date de publication:
19 Feb 2021
19 Feb 2021
Historique:
received:
13
09
2020
pubmed:
13
11
2020
medline:
13
11
2020
entrez:
12
11
2020
Statut:
ppublish
Résumé
Controlling the properties of supramolecular assemblies requires unveiling the specific interactions between their components. In the present work, the catalytic properties and structure of co-assemblies composed of a benzene-1,3,5-tricarboxamide (BTA) ligand coordinated to copper (the soldier) and seven enantiopure BTAs (the sergeants) have been determined. Whatever the sergeant, the enantioselectivity of the reaction is directly proportional to the optical purity of the supramolecular helices. More strikingly, the role played by the sergeant in the co-assembly process differs significantly: from almost pure intercalator (when it is incorporated in the stacks of the soldier and generates long homochiral helices) to pure chain capper (when it leads to the formation of partly helically biased and short assemblies). The former situation leads to optimal enantioselectivity for the catalytic system under study (58 % ee) while the latter situation leads to very low selectivity (8 % ee). The successful rationalization of this high and unexpected difference is crucial for the development of more efficient catalysts and more elaborate supramolecular systems.
Identifiants
pubmed: 33180372
doi: 10.1002/anie.202012457
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
4183-4191Subventions
Organisme : Consejo Nacional de Ciencia y Tecnologia
Organisme : China Scholarship Council
Informations de copyright
© 2020 Wiley-VCH GmbH.
Références
M. M. Green, M. P. Reidy, R. J. Johnson, G. Darling, D. J. Oleary, G. Willson, J. Am. Chem. Soc. 1989, 111, 6452-6454.
M. M. Green, J. W. Park, T. Sato, A. Teramoto, S. Lifson, R. L. B. Selinger, J. V. Selinger, Angew. Chem. Int. Ed. 1999, 38, 3138-3154;
Angew. Chem. 1999, 111, 3328-3345.
E. Yashima, K. Maeda, H. Iida, Y. Furusho, K. Nagai, Chem. Rev. 2009, 109, 6102-6211;
E. Yashima, N. Ousaka, D. Taura, K. Shimomura, T. Ikai, K. Maeda, Chem. Rev. 2016, 116, 13752-13990.
L. J. Prins, P. Timmerman, D. N. Reinhoudt, J. Am. Chem. Soc. 2001, 123, 10153-10163;
A. R. A. Palmans, J. A. J. M. Vekemans, E. E. Havinga, E. W. Meijer, Angew. Chem. Int. Ed. Engl. 1997, 36, 2648-2651;
Angew. Chem. 1997, 109, 2763-2765;
A. R. A. Palmans, E. W. Meijer, Angew. Chem. Int. Ed. 2007, 46, 8948-8968;
Angew. Chem. 2007, 119, 9106-9126;
L. Brunsveld, A. P. H. J. Schenning, M. A. C. Broeren, H. M. Janssen, J. A. J. M. Vekemans, E. W. Meijer, Chem. Lett. 2000, 29, 292-293;
L. Brunsfeld, B. G. G. Lohmeijer, J. A. J. M. Vekemans, E. W. Meijer, J. Inclusion Phenom. Macrocyclic Chem. 2001, 41, 61-64;
M. H. Liu, L. Zhang, T. Y. Wang, Chem. Rev. 2015, 115, 7304-7397.
J. Dubarle-Offner, J. Moussa, H. Amouri, B. Jouvelet, L. Bouteiller, M. Raynal, Chem. Eur. J. 2016, 22, 3985-3990.
S. H. Jung, J. Jeon, H. Kim, J. Jaworski, J. H. Jung, J. Am. Chem. Soc. 2014, 136, 6446-6452.
Y. X. Wang, X. J. Li, F. Li, W. Y. Sun, C. J. Zhu, Y. X. Cheng, Chem. Commun. 2017, 53, 7505-7508;
D. Yang, P. F. Duan, L. Zhang, M. H. Liu, Nat. Commun. 2017, 8, 15727-15735 ;
L. K. Ji, Y. T. Sang, G. H. Ouyang, D. Yang, P. F. Duan, Y. Q. Jiang, M. H. Liu, Angew. Chem. Int. Ed. 2019, 58, 844-848;
Angew. Chem. 2019, 131, 854-858;
P. Y. Li, B. Z. Lu, D. X. Han, P. F. Duan, M. H. Liu, M. Z. Yin, Chem. Commun. 2019, 55, 2194-2197;
A. Mukherjee, S. Ghosh, Chem. Eur. J. 2020, 26, 12874-12881.
A. Desmarchelier, X. Caumes, M. Raynal, A. Vidal-Ferran, P. W. N. M. van Leeuwen, L. Bouteiller, J. Am. Chem. Soc. 2016, 138, 4908-4916;
J. M. Zimbron, X. Caumes, Y. Li, C. M. Thomas, M. Raynal, L. Bouteiller, Angew. Chem. Int. Ed. 2017, 56, 14016-14019;
Angew. Chem. 2017, 129, 14204-14207;
Y. Li, X. Caumes, M. Raynal, L. Bouteiller, Chem. Commun. 2019, 55, 2162-2165;
Y. Li, L. Bouteiller, M. Raynal, ChemCatChem 2019, 11, 5212-5226;
Y. Li, A. Hammoud, L. Bouteiller, M. Raynal, J. Am. Chem. Soc. 2020, 142, 5676-5688.
S. Cantekin, T. F. A. de Greef, A. R. A. Palmans, Chem. Soc. Rev. 2012, 41, 6125-6137;
Y. Dorca, J. Matern, G. Fernández, L. Sánchez, Isr. J. Chem. 2019, 59, 869-880.
C. Kulkarni, E. W. Meijer, A. R. A. Palmans, Acc. Chem. Res. 2017, 50, 1928-1936.
J. J. van Gorp, J. A. J. M. Vekemans, E. W. Meijer, J. Am. Chem. Soc. 2002, 124, 14759-14769;
J. van Gestel, P. van der Schoot, M. A. J. Michels, Macromolecules 2003, 36, 6668-6673;
A. J. Wilson, J. van Gestel, R. P. Sijbesma, E. W. Meijer, Chem. Commun. 2006, 4404-4406;
M. M. J. Smulders, I. A. W. Filot, J. M. A. Leenders, P. van der Schoot, A. R. A. Palmans, A. P. H. J. Schenning, E. W. Meijer, J. Am. Chem. Soc. 2010, 132, 611-619;
M. M. J. Smulders, P. J. M. Stals, T. Mes, T. F. E. Paffen, A. P. H. J. Schenning, A. R. A. Palmans, E. W. Meijer, J. Am. Chem. Soc. 2010, 132, 620-626;
A. J. Markvoort, H. M. M. ten Eikelder, P. A. J. Hilbers, T. F. A. de Greef, E. W. Meijer, Nat. Commun. 2011, 2, 509;
H. M. M. ten Eikelder, A. J. Markvoort, T. F. A. de Greef, P. A. J. Hilbers, J. Phys. Chem. B 2012, 116, 5291-5301;
F. García, L. Sánchez, J. Am. Chem. Soc. 2012, 134, 734-742;
P. J. M. Stals, J. C. Everts, R. de Bruijn, I. A. W. Filot, M. M. J. Smulders, R. Martín-Rapún, E. A. Pidko, T. F. A. de Greef, A. R. A. Palmans, E. W. Meijer, Chem. Eur. J. 2010, 16, 810-821;
T. Kim, T. Mori, T. Aida, D. Miyajima, Chem. Sci. 2016, 7, 6689-6694;
Y. Li, L. Dubreucq, B. G. Alvarenga, M. Raynal, L. Bouteiller, Chem. Eur. J. 2019, 25, 10650-10661;
E. E. Greciano, J. Calbo, J. Buendía, J. Cerdá, J. Aragó, E. Ortí, L. Sánchez, J. Am. Chem. Soc. 2019, 141, 7463-7472.
H. M. M. ten Eikelder, B. Adelizzi, A. R. A. Palmans, A. J. Markvoort, J. Phys. Chem. B 2019, 123, 6627-6642;
L. N. J. de Windt, C. Kulkarni, H. M. M. ten Eikelder, A. J. Markvoort, E. W. Meijer, A. R. A. Palmans, Macromolecules 2019, 52, 7430-7438;
J. A. Berrocal, M. F. J. Mabesoone, M. G. Iglesias, A. Huizinga, E. W. Meijer, A. R. A. Palmans, Chem. Commun. 2019, 55, 14906-14909;
A. Das, G. Vantomme, A. J. Markvoort, H. M. M. ten Eikelder, M. Garcia-Iglesias, A. R. A. Palmans, E. W. Meijer, J. Am. Chem. Soc. 2017, 139, 7036-7044.
W. Zhang, W. S. Jin, T. Fukushima, T. Mori, T. Aida, J. Am. Chem. Soc. 2015, 137, 13792-13795;
J. Kang, D. Miyajima, T. Mori, Y. Inoue, Y. Itoh, T. Aida, Science 2015, 347, 646-651.
B. Adelizzi, A. Aloi, A. J. Markvoort, H. M. M. Ten Eikelder, I. K. Voets, A. R. A. Palmans, E. W. Meijer, J. Am. Chem. Soc. 2018, 140, 7168-7175;
R. van Buel, D. Spitzer, C. M. Berac, P. van der Schoot, P. Besenius, S. Jabbari-Farouji, J. Chem. Phys. 2019, 151, 014902.
G. Vantomme, G. M. ter Huurne, C. Kulkarni, H. M. M. ten Eikelder, A. J. Markvoort, A. R. A. Palmans, E. W. Meijer, J. Am. Chem. Soc. 2019, 141, 18278-18285;
E. Weyandt, G. M. ter Huurne, G. Vantomme, A. J. Markvoort, A. R. A. Palmans, E. W. Meijer, J. Am. Chem. Soc. 2020, 142, 6295-6303.
B. Adelizzi, N. J. Van Zee, L. N. J. de Windt, A. R. A. Palmans, E. W. Meijer, J. Am. Chem. Soc. 2019, 141, 6110-6121.
A. Desmarchelier, B. G. Alvarenga, X. Caumes, L. Dubreucq, C. Troufflard, M. Tessier, N. Vanthuyne, J. Idé, T. Maistriaux, D. Beljonne, P. Brocorens, R. Lazzaroni, M. Raynal, L. Bouteiller, Soft Matter 2016, 12, 7824-7838;
A. Desmarchelier, M. Raynal, P. Brocorens, N. Vanthuyne, L. Bouteiller, Chem. Commun. 2015, 51, 7397-7400.
Mixtures with a fraction of sergeant higher than 65 % led, for some S&S combinations, to viscous solutions that cannot be reliably analyzed.
For the mixtures with BTA Cha, this adapted fitting procedure gives similar results to the one previously employed in reference [8c].
T. F. A. De Greef, M. M. J. Smulders, M. Wolffs, A. P. H. J. Schenning, R. P. Sijbesma, E. W. Meijer, Chem. Rev. 2009, 109, 5687-5754.
Except for BTA Ala (see Material and Methods in the SI).
The role of BTA Nle in our study is somewhat different from that of the same sergeant in the study of Vantomme et al. (ref [15a]) for which BTA Nle was found to play the role of intercalator (respectively sequestrator) when present in a low (respectively high) fraction relatively to the soldier. This is likely due to the differences between the 2 systems under study (nature of the soldier, solvent).
R. P. Sijbesma, F. H. Beijer, L. Brunsveld, B. J. B. Folmer, J. H. K. K. Hirschberg, R. F. M. Lange, J. K. L. Lowe, E. W. Meijer, Science 1997, 278, 1601-1604;
F. Lortie, S. B. Boileau, L. Bouteiller, C. Chassenieux, F. Laupretre, Macromolecules 2005, 38, 5283-5287;
W. Knoben, N. A. M. Besseling, L. Bouteiller, A. C. Stuart, Phys. Chem. Chem. Phys. 2005, 7, 2390-2398;
W. Knoben, N. A. M. Besseling, M. A. Cohen Stuart, Macromolecules 2006, 39, 2643-2653;
W. Knoben, N. A. M. Besseling, M. A. C. Stuart, J. Chem. Phys. 2007, 126, 024907;
T. Pinault, C. Cannizzo, B. Andrioletti, G. Ducouret, F. Lequeux, L. Bouteiller, Langmuir 2009, 25, 8404-8407;
T. Pinault, B. Andrioletti, L. Bouteiller, Beilstein J. Org. Chem. 2010, 6, 869-875;
M. M. J. Smulders, M. M. L. Nieuwenhuizen, M. Grossman, I. A. W. Filot, C. C. Lee, T. F. A. de Greef, A. P. H. J. Schenning, A. R. A. Palmans, E. W. Meijer, Macromolecules 2011, 44, 6581-6587;
G. M. ter Huurne, P. Chidchob, A. G. Long, A. Martinez, A. R. A. Palmans, G. Vantomme, Chem. Eur. J. 2020, 26, 9964-9970;
S. C. Karunakaran, B. J. Cafferty, M. Peláez-Fernández, K. Neselu, I. Schmidt-Krey, A. Fernandez-Nieves, G. B. Schuster, N. V. Hud, Polym. Chem. 2018, 9, 5268-5277;
P. Besenius, J. Polym. Sci. Part A 2017, 55, 34-78;
S. C. Karunakaran, B. J. Cafferty, K. S. Jain, G. B. Schuster, N. V. Hud, ACS Omega 2020, 5, 344-349;
E. Weyandt, M. F. J. Mabesoone, L. N. J. De Windt, E. W. Meijer, A. R. A. Palmans, G. Vantomme, Org. Mater. 2020, 2, 129-142.
A. J. Boersma, J. E. Klijn, B. L. Feringa, G. Roelfes, J. Am. Chem. Soc. 2008, 130, 11783-11790.