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.
A mild and efficient
telescoped procedure for the stereoselective
alkenylation of simple, non-activated amides using LiCH2SiMe3 and carbonyl compounds as surrogates of alkenyllithium
reagents is reported. Our methodology relies on the formation of stable
tetrahedral intermediates, which, upon collapse into highly reactive
lithium enolates in a solvent-dependent fashion, allows for the assembly
of α,β-unsaturated ketones in a single synthetic operation
with high stereoselectivity.
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