A generally applicable silylation method for beta-hydroxylated primary, secondary, tertiary and even quaternary amines is presented. These aminoalcohols form 6-membered heterocycles under the influence of a reagent mixture consisting of 1,3-bis-(chloromethyl)-1,1,3,3-tetramethyldisilazane and chloromethyldimethyl-chlorosilane. Examples of analogue ring closures with a gamma-hydroxyamine and an alpha-amino acid are also given. The formation of the derivatives and their properties, are discussed, mainly from the viewpoint mass spectrometry.