Ruthenium‐Catalyzed Hydrosilylation of Aldehydes with Hydrooligosilanes

Ken-ichiro Kanno, Yasuhiro Sunaga, Soichiro Kyushin
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Abstract

Ruthenium‐catalyzed hydrosilylation of aldehydes with hydrooligosilanes is reported. Among the examined ruthenium catalysts, RuH2(CO)(PPh3)3 gave the best results. The reactions proceed with the Si–Si bonds preserved to afford the corresponding alkoxyoligosilanes in good yields. A series of aryl aldehydes with an electron‐withdrawing group is applicable, whereas those with an electron‐donating group are not suitable for the reaction. Mechanistic considerations suggest that the key points for the preservation of the Si–Si bonds are the formation of zero‐valent ruthenium species and the efficient coordination of the aldehyde to the ruthenium center prior to the oxidative addition of the Si–H bond.
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钌催化的氢寡硅烷醛氢硅烷化反应
报告了钌催化的醛与羟基硅烷的氢硅化反应。在所研究的钌催化剂中,RuH2(CO)(PPh3)3 的效果最好。反应在保留 Si-Si 键的情况下进行,以良好的收率得到相应的烷氧基寡硅烷。一系列带有取电子基团的芳基醛适用于该反应,而带有供电子基团的芳基醛则不适合该反应。机理分析表明,Si-Si 键得以保留的关键点在于零价钌物种的形成,以及在 Si-H 键氧化加成之前醛与钌中心的有效配位。
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