Trialkoxysilane Exchange: Scope, Mechanism, Cryptates and pH‐Response

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 comprehen...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2023-06, Vol.62 (26), p.e202304083-n/a
Main Authors: Hollstein, Selina, Erdmann, Philipp, Ulmer, Andreas, Löw, Henrik, Greb, Lutz, Delius, Max
Format: Article
Language:English
Subjects:
Alcohols
Alkoxysilanes
Computational Chemistry
Crown Ethers
Drug delivery
Drug Delivery Systems
Dynamic Covalent Chemistry
Exchanging
Host-Guest Chemistry
Hydrogen-Ion Concentration
Molecular structure
Salt effect
Salt Effects
Silicon
Solvents
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Summary: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. The exchange reaction of trialkoxysilanes with alcohols typically requires very harsh conditions and has therefore not been used for the self‐assembly of host‐guest systems. In this work, unexpected solvent and salt effects are described, rationalized and exploited for the synthesis of degradable supramolecular hosts.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202304083