Chemo- and Regioselective Anionic Fries Rearrangement Promoted by Lithium Amides under Aerobic Conditions in Sustainable Reaction Media |
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Authors: | Dr. Simone Ghinato Federica De Nardi Paola Bolzoni Dr. Achille Antenucci Dr. Marco Blangetti Prof. Cristina Prandi |
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Affiliation: | 1. Dipartimento di Chimica, Università degli Studi di Torino, Via Pietro Giuria 7, I-10125 Torino, Italy;2. Dipartimento di Chimica, Università degli Studi di Torino, Via Pietro Giuria 7, I-10125 Torino, Italy These authors contributed equally to this work. |
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Abstract: | A straightforward and efficient protocol to promote the metalation/anionic Fries rearrangements of O-aryl carbamates, using for the first time a lithium amide as metalating agent under aerobic/ambient-friendly reaction conditions, is reported. This approach enables the sustainable preparation of salicylamide derivatives with high levels of chemoselectivity within ultrafast reaction times, working at room temperature in the presence of air/moisture, and using environmentally responsible cyclopentyl methyl ether as a solvent. Furthermore, the regioselective manipulation of O-2-tolyl carbamates has been accomplished using interchangeably alkyllithiums or lithium amides, with an unexpected beneficial contribution from the employment of biorenewable protic eutectic mixtures as non-innocent reaction media. |
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Keywords: | alkali metal Fries rearrangement lithium amide metalation sustainable chemistry |
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