Johannes Schöntag, Theresa Hettiger, William Roberts, Marcus Scheele, Markus Ströbele and Holger F. Bettinger*,
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Rearrangement Cascade Initiated by Nucleophilic Benzyne Attack on 3,6-Di(2-pyridyl)-1,2-diazines
Aryne intermediates in synthetic organic chemistry offer versatile routes to complex heterocyclic structures that are valuable in pharmaceuticals and materials science. We present a one-step aryne-mediated reaction to synthesize pyrido[1,2-a]indoles interconnected through vinylene or 1,2-phenylene linkers to pyridotriazoles using 2-pyridyl-substituted pyridazines and phthalazines as confirmed via single-crystal X-ray crystallography and NMR spectroscopy. This unexpected rearrangement proceeds under mild conditions. Considering that five bonds are broken and three new bonds are formed in the reaction between 3,6-di-2-pyridyl-1,2,4,5-tetrazine and benzyne, the yield of 16% is fair. Electron-rich substituents on aryne precursors destabilized the products, while electron-deficient substituents offered some stability improvements. DFT studies could reveal the mechanism of this rearrangement.
期刊介绍:
ACS Organic & Inorganic Au is an open access journal that publishes original experimental and theoretical/computational studies on organic organometallic inorganic crystal growth and engineering and organic process chemistry. Short letters comprehensive articles reviews and perspectives are welcome on topics that include:Organic chemistry Organometallic chemistry Inorganic Chemistry and Organic Process Chemistry.