路易斯酸促进的硅氧烷键形成：一种非水解溶胶-凝胶过程及皮尔斯-鲁宾什泰因反应。

Siloxane-Bond Formation Promoted by Lewis Acids: A Nonhydrolytic Sol-Gel Process and the Piers-Rubinsztajn Reaction.

作者信息

Wakabayashi Ryutaro, Kuroda Kazuyuki

机构信息

Department of Applied Chemistry, Waseda University, Ohkubo-3, Shinjuku-ku, Tokyo 169-8555 (Japan), Fax: (+81) 3-5286-3199 http://www.waseda.jp/sem-kuroda_lab/.

Kagami Memorial Research Institute for Materials, Science and Technology, Waseda University, Nishiwaseda-2, Shinjuku-ku, Tokyo 169-0051 (Japan).

出版信息

Chempluschem. 2013 Aug;78(8):764-774. doi: 10.1002/cplu.201300027. Epub 2013 Jul 15.

DOI:10.1002/cplu.201300027

PMID:31986688

Abstract

Siloxane formation reactions of both the nonhydrolytic sol-gel process and Piers-Rubinsztajn reaction can be integrated as Lewis acid promoted siloxane syntheses without involving silanol groups. The former was developed in the field of inorganic materials chemistry and the latter was initiated in polymer chemistry. We have realized both reactions are quite similar, in terms of 1) the nonhydrolytic reaction, 2) the use of alkoxysilanes, 3) the group-exchange reactions competing with the siloxane formation, and 4) the proposed reaction mechanisms. This Minireview focuses on the above two reactions. The evolution of both reactions should realize a more sophisticated molecular design of siloxane compounds, which surely contributes to the development of advanced functional materials.

摘要

非水解溶胶-凝胶过程和皮尔斯-鲁宾斯泰因反应的硅氧烷形成反应都可以整合为路易斯酸促进的硅氧烷合成，而无需涉及硅醇基团。前者是在无机材料化学领域发展起来的，后者则始于高分子化学领域。我们已经认识到，就1）非水解反应、2）烷氧基硅烷的使用、3）与硅氧烷形成竞争的基团交换反应以及4）所提出的反应机理而言，这两种反应非常相似。本综述聚焦于上述两种反应。这两种反应的发展应能实现对硅氧烷化合物更精细的分子设计，这必将有助于先进功能材料的开发。