Palladium-Catalyzed β-Elimination of Aminoboranes from (Aminomethylsilyl)boranes Leading to the Formation of Silene Dimers,Organometallics

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Palladium-Catalyzed β-Elimination of Aminoboranes from (Aminomethylsilyl)boranes Leading to the Formation of Silene Dimers
Organometallics ( IF 2.5 ) Pub Date : 2017-10-30 00:00:00 , DOI: 10.1021/acs.organomet.7b00695
Toshimichi Ohmura ₁ , Hiroki Nishiura ₁ , Michinori Suginome ₁

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Silylboronic esters bearing a N,N-dialkylaminomethyl group on the silicon atoms were synthesized and used in palladium-catalyzed reactions. Five silylboronic esters were synthesized through a reaction of the [(N,N-dialkylaminomethyl)diorganosilyl]lithiums with i-PrOB(pin). An addition reaction of the silylboronic ester to ethynylbenzene (silaboration) took place efficiently by a phosphine- and isocyanide-free palladium catalyst to give (E)-1-silyl-2-boryl-1-phenylethene in a regio- and stereoselective manner. On the other hand, the silylboronic esters underwent β-elimination reactions in the presence of a palladium catalyst and styrene to afford 1,3-disilacyclobutanes and aminoboranes in good yields. This may be due to the generation of silene intermediates during the reaction. It should be noted that use of styrene as a ligand was essential for the generation of the silene species.

中文翻译：

钯催化从（氨基甲基甲硅烷基）硼烷中消除氨基硼烷，导致形成硅二聚体

合成了在硅原子上带有N，N-二烷基氨基甲基的甲硅烷基硼酸酯，并将其用于钯催化的反应中。通过[（N，N-二烷基氨基甲基）二有机甲硅烷基]锂与i -PrOB（pin）的反应合成了五种甲硅烷基硼酸酯。甲硅烷基硼酸酯与乙炔基苯的加成反应（分解）通过无膦和异氰化物的钯催化剂有效地进行，从而得到（E）-1-硅烷基-2-硼基-1-苯基乙烯以区域和立体选择性的方式。另一方面，甲硅烷基硼酸酯在钯催化剂和苯乙烯存在下进行β-消除反应，以高收率得到1，3-二硅环丁烷和氨基硼烷。这可能是由于在反应过程中产生了硅中间体。应当指出，使用苯乙烯作为配体对于生成硅物质是必不可少的。

更新日期：2017-10-30

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