Copper(I)-Catalized Cross-Coupling of Organosilicon Compounds Utilizing Fluoride Ion Free Activators

2016 Fiscal Year Final Research Report

• Project/Area Number: 26410037
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Tokyo University of Agriculture and Technology
• Principal Investigator: TSUBOUCHI Akira 東京農工大学, 工学(系)研究科(研究院), 助教 (40272637)
• Project Period (FY): 2014-04-01 – 2017-03-31
• Keywords: クロスカップリング / ケイ素化合物 / 有機銅化合物 / 環状シリカート / 環状シリカート / 銅(I)アルコキシド / 環状シリカート

Outline of Final Research Achievements

A fluoride-ion-free activation for the Si-C bond has been developed to achieve the copper(I) promoted cross-coupling of aryl- and alkenyldimethylsilanes with organic halides using a double activation of the silicon atom. In this activation, the formation of cyclic silicates by intramolecular coordination of copper alkoxide facilitates the transmetallation with copper(I) and simulteniously the coordination of the oxygen atom to the silicon atom activates the Si-C bond. Thus, we have found that fluoride-free cross-coupling of aryl- and alkenyldimethylsilanes with organic halides proceeded in the presence of monocopper(I) alkoxide of ethylene glycol. In addition, we have developed a copper(I) iodide/sodium hydride/ethylene glycol system as a new activator, which promoted the reaction of aryl- and alkenyldimethylsilanes with C(sp3)-X electrophiles bearing a beta-hydrogen to produce the cross- coupling products at ambient temperature within a short period of time.

Free Research Field

有機合成化学