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Title: A highly strained Al-Al σ-bond in dianionic aluminum analog of oxirane for molecule activation
Authors: Koshino, Kota
Kinjo, Rei
Keywords: Science::Chemistry
Issue Date: 2021
Source: Koshino, K. & Kinjo, R. (2021). A highly strained Al-Al σ-bond in dianionic aluminum analog of oxirane for molecule activation. Journal of the American Chemical Society, 143(43), 18172-18180.
Project: MOE2018-T2-2-048(S)
Journal: Journal of the American Chemical Society
Abstract: 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.
ISSN: 0002-7863
DOI: 10.1021/jacs.1c07389
Schools: School of Physical and Mathematical Sciences 
Rights: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see
Fulltext Permission: open
Fulltext Availability: With Fulltext
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