A methodology to access Z-1-silyl-2-aluminyl-disubstituted olefins is developed. It relies on the uncatalyzed ring opening of silacyclopropenes in the presence of a stoichiometric amount of trimethylaluminum. The resulting heterosubstituted alkenes exhibit a particular interaction between the electron-rich [Si–CH₃] moiety and the electron-deficient diorganoaluminyl group, resulting in similar geometrical features due to the proximity of these two centers. This interaction is rationalized using experimental and theoretical descriptors. The regioselectivity and functional tolerance of the methylalumination were also studied in the case of unsymmetrical silacyclopropenes, and the methodology ultimately transposed to the synthesis of a polymeric organoalane incorporating tricoordinated aluminum centers.

中文翻译：

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硅烷环丙烯的区域特异性甲基化：Z-1-硅烷基-2-铝基-二取代烯烃的获取


开发了一种获取 Z-1-硅烷基-2-铝基-二取代烯烃的方法。它依赖于硅环丙烯在化学计量量的三甲基铝存在下未催化的开环。所得的异质取代烯烃在富电子 [Si-CH₃] 部分和缺电子的二有机铝基团之间表现出特殊的相互作用，由于这两个中心靠近，因此产生了相似的几何特征。这种互动使用实验和理论描述符进行合理化。在不对称硅烷环丙烯的情况下，还研究了甲基化的区域选择性和功能耐受性，该方法最终转化为合成包含三配位铝中心的聚合物有机烷。