Reactivity of Triethylborane towards Di(alkyn-1-yl)(chloro)silanes. Competition between 1,1-Organoboration and 1,2-Hydroboration
Reactivity of Triethylborane towards Di(alkyn-1-yl)(chloro)silanes. Competition between 1,1-Organoboration and 1,2-Hydroboration
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三乙基硼烷对二(炔-1-基)(氯)硅烷的反应性。
DOI：
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发表时间：
2009
期刊：
影响因子：
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通讯作者：
B. Wrackmeyer
中科院分区：
文献类型：
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作者：
Ezzat Khan;Stefan Bayer;B. Wrackmeyer
二(烷基-1-基)(氯)硅烷、HSi(Cl)(C≡C-R)2、R1Si(Cl)(C≡C-R)2或HSi(Cl)-(C≡C-R)C≡C-Rʹ与过量的三乙基硼烷BEt3的反应在100-120℃下缓慢进行(几天)。HSi(Cl)(C≡C-R)2或HSi(Cl)(C≡C-R)C≡C-Rʹ的两次1，1-有机取代导致硅烯，而不依赖于R=NBU、TBU、Me3。这为在硅原子上同时携带氢和氯的硅烷提供了最直接的方法。然而，在R=Ph的情况下，BEt3作为1，2-氢化硼试剂在分子间第一步反应，生成1-硅环丁烯衍生物。用多核核磁共振波谱(1H、11B、13C和29Si)对所有硅烷和1-硅环丁烯衍生物进行了表征。用9-硼二环[3.3.1]正庚烷，9-BBN作为1，2-氢化硼试剂合成了类似的1-硅环丁烯衍生物。三乙基硼烷与二(烷基-1-基)(氯)硅烷的反应活性。1，1-有机硼与1，2-硼氢化的竞争
Reactions of di(alkyn-1-yl)(chloro)silanes, HSi(Cl)(C≡C-R)2, R1Si(Cl)(C≡C-R)2 or HSi(Cl)-(C≡C-R)C≡C-Rʹ, with an excess of triethylborane, BEt3, proceed slowly (several days) at 100 -120 °C. Twofold 1,1-organoboration of HSi(Cl)(C≡C-R)2 or HSi(Cl)(C≡C-R)C≡C-Rʹleads tosiloles, independent of R = nBu, tBu, SiMe3. This provides the most straightforward way to silolesbearing both a hydrogen and a chlorine at the silicon atom. However, in the cases of R = Ph, BEt3 actsas 1,2-hydroborating reagent in the intermolecular first step of the reaction, leading to 1-silacyclobutene derivatives. All siloles and 1-silacyclobutene derivatives were characterized by multinuclear NMR spectroscopy (1H, 11B, 13C and 29Si). Comparable 1-silacyclobutene derivatives were formed using 9-borabicyclo[3.3.1]nonane, 9-BBN, as a well established 1,2- hydroborating reagent Graphical Abstract Reactivity of Triethylborane towards Di(alkyn-1-yl)(chloro)silanes. Competition between 1,1-Organoboration and 1,2-Hydroboration