Ghinato Simone, De Nardi Federica, Bolzoni Paola, Antenucci Achille, Blangetti Marco, Prandi Cristina
Dipartimento di Chimica, Università degli Studi di Torino, Via Pietro Giuria 7, I-10125, Torino, Italy.
Chemistry. 2022 Jul 1;28(37):e202201154. doi: 10.1002/chem.202201154. Epub 2022 May 19.
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.
报道了一种直接且高效的方法，用于促进O-芳基氨基甲酸酯的金属化/阴离子弗里斯重排，该方法首次在有氧/环境友好的反应条件下使用锂酰胺作为金属化剂。这种方法能够在超快的反应时间内，在室温下、有空气/水分存在的情况下，以对环境负责的环戊基甲基醚作为溶剂，实现水杨酰胺衍生物的可持续制备，并具有高度的化学选择性。此外，使用烷基锂或锂酰胺可互换地实现对O-2-甲苯基氨基甲酸酯的区域选择性操作，使用生物可再生质子共晶混合物作为非惰性反应介质会产生意想不到的有益效果。
