Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 143, Issue 43, Pages 18172-18180Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c07389
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- Nanyang Technological University (NTU)
- Singapore Ministry of Education [MOE2018-T2-2-048(S)]
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This study presents the synthesis of a dianionic dialane based on the Al2O three-membered ring scaffold, with a highly strained Al-Al sigma-bond. This compound can react with unsaturated substrates to form heterocycles, and selectively activate an arene ring C-C bond for further reactions.
Since aluminum is the most electropositive element among the p-block elements, the construction of molecules bearing a dianionic Al-Al sigma-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 sigma-bond. 2 readily reacts with the unsaturated substrates such as isocyanide, ethylene, and ketone, concomitant with the cleavage of the Al-Al sigma-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 sigma-bond cleavage, dearomative Al-C bond formation, subsequent sigmatropic [1,3]shifts, and a pericyclic reaction.
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