RUTHENIUM-CATALYZED OXIDATIONS FOR SELECTIVE SYNTHESES OF KETONES ANDACYL CYANIDES - SELECTIVE ACYLATION OF AMINO-COMPOUNDS WITH ACYL CYANIDES

Oxidation of alcohols to the corresponding carbonyl compounds with ter t-butyl hydroperoxide in the presence of dichlorotris(triphenylphosphi ne)ruthenium catalyst gives the corresponding carbonyl compounds with high efficiency. This method can be applied to the oxidation of cyanoh ydrins to give acyl cyanides which are versatile synthetic intermediat es. Acylation of amino compounds with acyl cyanides thus obtained proc eeds chemoselectively. Thus, the reaction of amino alcohols with acyl cyanides gives N-acylated products exclusively. In the similar N-acyla tion of polyamines primary amines are selectively acylated in the pres ence of secondary amines. These reactions are highly useful for the sy nthesis of spermidine and spermine alkaloids such as spermidine sidero phores. Dimeric cyclocoupling reaction of diacyl cyanides such as iso- and terephthaloyl cyanides with polyamines can be performed under the similar reaction conditions to give the corresponding polyazamacrocyc les with high efficiency.