A Highly Strained Al–Al σ-Bond in Dianionic Aluminum Analog of Oxirane for Molecule Activation,Journal of the American Chemical Society

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A Highly Strained Al–Al σ-Bond in Dianionic Aluminum Analog of Oxirane for Molecule Activation
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-10-26 , DOI: 10.1021/jacs.1c07389
Kota Koshino ₁ , Rei Kinjo ₁

Affiliation

Since aluminum is the most electropositive element among the p-block elements, the construction of molecules bearing a dianionic Al–Al σ-bond is inherently highly challenging. Herein, we report the first synthesis of a dianionic dialane(6) 2 based on the Al₂O three-membered ring scaffold, namely, an aluminum analog of oxirane. The structure of 2 has been unambiguously ascertained by spectroscopic analysis as well as X-ray crystallography, and computational studies revealed that 2 bears a highly strained Al–Al σ-bond. 2 readily reacts with the unsaturated substrates such as isocyanide, ethylene, and ketone, concomitant with the cleavage of the Al–Al σ-bond under mild conditions, leading to the four- and five-membered heterocycles 3–5. Furthermore, the reaction of 2 with two molecules of benzonitrile (PhCN) furnishes a seven-membered heterocycle 6, resulting from the C–C coupling reaction of PhCN. We further delineate that 2 selectively activates an arene ring C–C bond of biphenylene, rendering a di-Al-substituted benzo[8]annulene derivative 7. Preliminary computational studies propose that the stepwise reaction mechanism involves the Al–Al σ-bond cleavage, dearomative Al–C bond formation, subsequent sigmatropic [1,3]shifts, and a pericyclic reaction.

中文翻译：

用于分子活化的环氧乙烷双阴离子铝模拟物中的高应变 Al-Al σ-键

由于铝是 p 嵌段元素中最具正电性的元素，因此构建带有双阴离子 Al-Al σ 键的分子本质上是极具挑战性的。在此，我们报告了基于 Al ₂ O 三元环支架的双阴离子二烷 (6) 2的首次合成，即环氧乙烷的铝类似物。2的结构已通过光谱分析和 X 射线晶体学明确确定，计算研究表明2具有高度应变的 Al-Al σ-键。2容易与异氰化物、乙烯和酮等不饱和底物反应，伴随着 Al-Al σ-键在温和条件下断裂，生成四元和五元杂环3-5。此外，2与两分子苯甲腈 (PhCN) 的反应提供了一个七元杂环6，这是由 PhCN 的 C-C 偶联反应产生的。我们进一步描述了2选择性地激活了联苯的芳烃环 C-C 键，从而产生了二铝取代的苯并[8] 环烯衍生物7. 初步计算研究表明，逐步反应机制涉及 Al-Al σ-键断裂、脱芳烃 Al-C 键形成、随后的 sigmatropic [1,3] 位移和周环反应。

更新日期：2021-11-03

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