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Trialkoxysilane Exchange: Scope,Mechanism, Cryptates and pH-Response |
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| Authors: | Selina Hollstein Philipp Erdmann Andreas Ulmer Dr. Henrik Löw Prof. Dr. Lutz Greb Prof. Dr. Max von Delius |
| Affiliation: | 1. Institute of Organic Chemistry, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm, Germany;2. Anorganisch-Chemisches Institut, Ruprecht-Karls-Universität, Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany These authors contributed equally to this work.;3. Institute of Organic Chemistry, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm, Germany These authors contributed equally to this work.;4. Anorganisch-Chemisches Institut, Ruprecht-Karls-Universität, Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany |
| Abstract: | The dynamic covalent chemistry (DCvC) of the Si−O bond holds unique opportunities, but has rarely been employed to assemble discrete molecular architectures. This may be due to the harsh conditions required to initiate exchange reactions at silicon in aprotic solvents. Herein, we provide a comprehensive experimental and computational account on the reaction of trialkoxysilanes with alcohols and identify mild conditions for rapid exchange in aprotic solvents. Substituent, solvent and salt effects are uncovered, understood and exploited for the construction of sila-orthoester cryptates. A sharp, divergent pH-response of the obtained cages renders this substance class attractive for future applications well beyond host-guest chemistry, for instance, in drug delivery. |
| Keywords: | Alkoxysilanes Computational Chemistry Dynamic Covalent Chemistry Host-Guest Chemistry Salt Effects |