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An uncatalyzed method for the silylation of alcohols and phenols with HMDS in CH3NO2 at rt is developed. A diverse range of aromatic and aliphatic alcohols as well as phenols undergo the silylation in very short reaction time with excellent yield. The uncatalyzed reaction requires neither elevated temperature nor high pressure for the silylation.

Graphical abstract: Catalyst-free silylation of alcohols and phenols by promoting HMDS in CH3NO2 as solvent

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