Disiloxane Synthesis Based on Silicon-Hydrogen Bond Activation using Gold and Platinum on Carbon in Water or Heavy Water

被引：26

作者：

Sawama, Yoshinari ^{[1
]}

Masuda, Masahiro ^{[1
]}

Yasukawa, Naoki ^{[1
]}

Nakatani, Ryosuke ^{[1
]}

Nishimura, Shumma ^{[1
]}

Shibata, Kyoshiro ^{[1
]}

Yamada, Tsuyoshi ^{[1
]}

Monguchi, Yasunari ^{[1
]}

Suzuka, Hiroyasu ^{[2
]}

Takagi, Yukio ^{[3
]}

Sajiki, Hironao ^{[1
]}

机构：

[1] Gifu Pharmaceut Univ, Organ Chem Lab, 1-25-4 Daigaku Nishi, Gifu 5011196, Japan

[2] NE Chemcat Corp, Catalyst Dev Ctr, 25-3 Koshindaira, Bando, Ibaraki 3060608, Japan

[3] NE Chemcat Corp, Catalyst Dev Ctr, 678 Ipponmatsu, Numazu, Shizuoka 4100314, Japan

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2016年 / 81卷 / 10期

关键词：

D EXCHANGE-REACTION; HYDROLYTIC OXIDATION; CATALYZED OXIDATION; MIXED CATALYST; H/D EXCHANGE; SILANES; EFFICIENT; ORGANOSILANES; COMPLEXES; REDUCTION;

D O I：

10.1021/acs.joc.6b00556

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Disiloxanes possessing a silicon-oxygen linkage are important as frameworks for functional materials and coupling partners for Hiyama-type cross coupling. We found that disiloxanes were effectively constructed of hydrosilanes catalyzed by gold on carbon in water as the solvent and oxidant in association with the emission of hydrogen gas at room temperature. The present oxidation could proceed via various reaction pathways, such as the hydration of hydrosilane into silanol, dehydrogenative coupling of hydrosilane into disilane, and the subsequent corresponding reactions to disiloxane. Additionally, the platinum on carbon catalyzed hydrogen deuterium exchange reaction of arylhydrosilanes as substrates in heavy water proceeded on the aromatic nuclei at 80 degrees C with high deuterium efficiency and high regioselectivity at the only meta and para positions of the aromatic silicon bond to give the deuterium-labeled disiloxanes.

引用

页码：4190 / 4195

页数：6