Cascade-Reaction Leading to an Intramolecular [2 + 4] Cycloaddition of a Phenyl Group by a Reactive Ge═Si Double Bond.,Inorganic Chemistry

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Cascade-Reaction Leading to an Intramolecular [2 + 4] Cycloaddition of a Phenyl Group by a Reactive Ge═Si Double Bond.
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-04-15 , DOI: 10.1021/acs.inorgchem.0c00379
Tanja Kunz ₁ , Claudio Schrenk ₁ , Andreas Schnepf ₁

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The reaction of GeCl2·dioxane with 2 equiv of the thiolate LiSHyp [Hyp = Si(SiMe3)3] yields the germanide (12-crown-4)2Li[Ge(SHyp)3] (1). A small structural variation in the substituent leads to a completely different result because the reaction of GeCl2·dioxane with 2 equiv of the thiolate KSHypPh3 [HypPh3 = Si(SiMe3)2(SiPh3)] in toluene yields the unexpected compound [Ph3Si][Me3Si]Ge[{(C6H5)Ph2Si}{SiMe3}2SiS]Si[SSiMe3] (2) in high yield. The reaction cascade to give 2 includes several rearrangement reactions and an intramolecular [2 + 4] cycloaddition of a phenyl ring. The syntheses and molecular structures of both compounds are presented, together with quantum-chemical calculations and NMR measurements, to enlighten the reaction mechanism behind the formation of 2.

中文翻译：

级联反应通过反应性Ge═Si双键导致苯基的分子内[2 + 4]环加成。

GeCl2·二恶烷与2当量的硫醇盐LiSHyp [Hyp = Si（SiMe3）3]反应生成锗化物（12-crown-4）2Li [Ge（SHyp）3]（1）。取代基的微小结构变化会导致完全不同的结果，因为GeCl2·二恶烷与甲苯中2当量的硫醇盐KSHypPh3 [HypPh3 = Si（SiMe3）2（SiPh3）]的反应会产生意外的化合物[Ph3Si] [Me3Si高产率的] Ge [{（（C6H5）Ph2Si} {SiMe3} 2SiS] Si [SSiMe3]（2）。级联生成2的反应包括几个重排反应和苯环的分子内[2 + 4]环加成。介绍了这两种化合物的合成和分子结构，以及量子化学计算和NMR测量，以启发2形成背后的反应机理。

更新日期：2020-04-15

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