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Synthesis of Macro(alkoxyamines) via Hydroboration of Polyolefins with Subsequent Nitroxide Oxidation for Controlled NMP



A novel method for the synthesis of alkoxyamines that are subsequently used as initiator/regulators for NMP is reported. This method can be applied to low-molecular-weight olefins as well as to macromolecules containing alkene moieties to form poly(alkoxyamines). The reaction sequence comprises hydroboration of olefins with catecholborane followed by oxidation of alkylborane intermediates using nitroxides in the presence of methyl vinyl ketone to ultimately yield alkoxyamines that serve as suitable initiators for NMP. The first application of these alkoxyamines for the preparation of comb and star polymers is presented.

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