Self-assembled nanospheres with multiple endohedral binding sites pre-organize catalysts and substrates for highly efficient reactions

作者: Qi-Qiang Wang , Sergio Gonell , Stefan H. A. M. Leenders , Maximilian Dürr , Ivana Ivanović-Burmazović

DOI: 10.1038/NCHEM.2425

关键词:

摘要: Tuning reagent and catalyst concentrations is crucial in the development of efficient catalytic transformations. In enzyme-catalysed reactions substrate bound-often by multiple non-covalent interactions-in a well-defined pocket close to active site enzyme; this pre-organization facilitates highly Here we report an artificial system that co-encapsulates catalysts substrates within confined space defined M12L24 nanosphere contains 24 endohedral guanidinium-binding sites. Cooperative binding means sulfonate guests are bound much more strongly than carboxylates. This difference has been used fix gold-based firmly, with remaining sites left pre-organize substrates. strategy was applied Au(I)-catalysed cyclization acetylenic acid enol lactone which resulted higher reaction rates. We also found encapsulated sulfonate-containing Au(I) did not convert neutral (acid) substrates, so could have potential substrate-selective catalysis base-triggered on/off switching catalysis.

参考文章(42)
William M. Hart-Cooper, Kristen N. Clary, F. Dean Toste, Robert G. Bergman, Kenneth N. Raymond, Selective Monoterpene-like Cyclization Reactions Achieved by Water Exclusion from Reactive Intermediates in a Supramolecular Catalyst Journal of the American Chemical Society. ,vol. 134, pp. 17873- 17876 ,(2012) , 10.1021/JA308254K
Dong Li, Wu Zhou, Kai Landskron, Sota Sato, Christopher J. Kiely, Makoto Fujita, Tianbo Liu, Viral-capsid-type vesicle-like structures assembled from M12L24 metal-organic hybrid nanocages. Angewandte Chemie. ,vol. 50, pp. 5182- 5187 ,(2011) , 10.1002/ANIE.201007829
Timothy J. Brown, Dieter Weber, Michel R. Gagné, Ross A. Widenhoefer, Mechanistic analysis of gold(I)-catalyzed intramolecular allene hydroalkoxylation reveals an off-cycle bis(gold) vinyl species and reversible C-O bond formation. Journal of the American Chemical Society. ,vol. 134, pp. 9134- 9137 ,(2012) , 10.1021/JA303844H
Michael D. Best, Suzanne L. Tobey, Eric V. Anslyn, Abiotic guanidinium containing receptors for anionic species Coordination Chemistry Reviews. ,vol. 240, pp. 3- 15 ,(2003) , 10.1016/S0010-8545(02)00256-4
Andrew D. Burrows, Ross W. Harrington, Mary F. Mahon, Simon J. Teat, Structural Manipulation of Hydrogen Bond Networks Using Sulfonated Phosphane Ligands and Their Complexes: Competition and Interplay Between Strong and Weak Hydrogen Bonds European Journal of Inorganic Chemistry. ,vol. 2003, pp. 1433- 1439 ,(2003) , 10.1002/EJIC.200390186
Christophe Desmarets, Thierry Ducarre, Marie Rager, Geoffrey Gontard, Hani Amouri, Self-Assembled M 2 L 4 Nanocapsules: Synthesis, Structure and Host-Guest Recognition Toward Square Planar Metal Complexes Materials. ,vol. 7, pp. 287- 301 ,(2014) , 10.3390/MA7010287
Hani Amouri, Christophe Desmarets, Jamal Moussa, Confined nanospaces in metallocages: guest molecules, weakly encapsulated anions, and catalyst sequestration. Chemical Reviews. ,vol. 112, pp. 2015- 2041 ,(2012) , 10.1021/CR200345V
Richard J. Hooley, Julius Rebek, Chemistry and Catalysis in Functional Cavitands Chemistry & Biology. ,vol. 16, pp. 255- 264 ,(2009) , 10.1016/J.CHEMBIOL.2008.09.015
Alessandra Cavarzan, Alessandro Scarso, Paolo Sgarbossa, Giorgio Strukul, Joost N. H. Reek, Supramolecular control on chemo- and regioselectivity via encapsulation of (NHC)-Au catalyst within a hexameric self-assembled host. Journal of the American Chemical Society. ,vol. 133, pp. 2848- 2851 ,(2011) , 10.1021/JA111106X
Z. Jane Wang, Kristen N. Clary, Robert G. Bergman, Kenneth N. Raymond, F. Dean Toste, A supramolecular approach to combining enzymatic and transition metal catalysis Nature Chemistry. ,vol. 5, pp. 100- 103 ,(2013) , 10.1038/NCHEM.1531