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10 Feb 13:43

Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal–Organic Frameworks

by Liang Feng, Shuai Yuan, Liang-Liang Zhang, Kui Tan, Jia-Luo Li, Angelo Kirchon, Ling-Mei Liu, Peng Zhang, Yu Han, Yves J. Chabal and Hong-Cai Zhou

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.7b12916
15 Sep 23:58

Protecting and Leaving Functions of Trimethylsilyl Groups in Trimethylsilylated Silicates for the Synthesis of Alkoxysiloxane Oligomers

by Masashi Yoshikawa, Yasuhiro Tamura, Ryutaro Wakabayashi, Misa Tamai, Atsushi Shimojima, Kazuyuki Kuroda

Abstract

The concept of protecting groups and leaving groups in organic synthesis was applied to the synthesis of siloxane-based molecules. Alkoxy-functionalized siloxane oligomers composed of SiO4, RSiO3, or R2SiO2 units were chosen as targets (R: functional groups, such as Me and Ph). Herein we describe a novel synthesis of alkoxysiloxane oligomers based on the substitution reaction of trimethylsilyl (TMS) groups with alkoxysilyl groups. Oligosiloxanes possessing TMS groups were reacted with alkoxychlorosilane in the presence of BiCl3 as a catalyst. TMS groups were substituted with alkoxysilyl groups, leading to the synthesis of alkoxysiloxane oligomers. Siloxane oligomers composed of RSiO3 and R2SiO2 units were synthesized more efficiently than those composed of SiO4 units, suggesting that the steric hindrance around the TMS groups of the oligosiloxanes makes a difference in the degree of substitution. This reaction uses TMS groups as both protecting and leaving groups for SiOH/SiO− groups.

Thumbnail image of graphical abstract

The concept of protecting groups in organic synthesis is applied to the synthesis of siloxane oligomers with alkoxy groups. Several alkoxysiloxane oligomers were successfully synthesized by substitution of trimethysilyl groups with alkoxysilyl groups.