Development of the Dioxasilepanyl Group Si(pan): A Seven-Membered Dialkoxysilane Unit

Abstract

This Account describes the development and applications of a new cyclic dialkoxysilane unit, Si(pan), featuring a unique seven-membered ring system. Although alkoxysilanes are invaluable functional groups in organic synthesis, they typically exhibit an inherent trade-off between stability and reactivity. The Si(pan) unit circumvents this limitation through its distinctive structural features: a tetramethylated seven-membered ring that confers enhanced kinetic stability while preserving the requisite Lewis acidity at the silicon center. We demonstrate that Si(pan)-containing compounds exhibit exceptional stability under diverse reaction conditions while maintaining high reactivity toward selective transformations. The synthetic utility of this silicon unit is demonstrated through efficient protocols, including arylalkali-metal substitution reactions, C–H silylation, and transition-metal-catalyzed cross-coupling reactions. Additionally, we have developed a new silylation methodology by exploiting in situ generated silylpotassium species derived from the Si(pan)Me dimer. Furthermore, we describe the development of a trialkoxysilyl unit, Si(pan)OMe, enabling the controlled synthesis of unsymmetrical diaryldialkoxysilanes and serving as a practical surrogate for trimethoxysilanes. These findings establish Si(pan) as a versatile silicon-based functional group that facilitates previously challenging transformations in organosilicon chemistry.

1 Introduction

2 Chemistry of Si(pan)Me

3 Chemistry of Si(pan)OR

4 Conclusion

Key words

alkoxysilanes - silicon - silanol - siloxane - dioxasilepanyl - Si(pan)

Publikationsverlauf

Eingereicht: 18. März 2025

Angenommen nach Revision: 10. April 2025

Accepted Manuscript online:
10. April 2025

Artikel online veröffentlicht:
14. Mai 2025

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