Tethered alkoxyamines

Tethered alkoxyamines were also obtained in situ following a two-step procedure. First, 3-(trimethoxysilyl)propyl methacrylate (TSPMA) was attached to the surface. Then, the methacrylate function was allowed to react, under heating, with AIBN in the presence of TEMPO to afford the corresponding alkoxyamines. From this alkoxyamine-coated silicon, PS and poly(2-hydroxyethyl methacrylate) (HEMA) were then successfully prepared [20]. The novelty of this report is that micropatteming of the silicon surface was controlled by a combination of SI-NMP and Sl-ATRP. The ATRP initiator was covalently immobilized via UV-induced hydrosilylation of 4-vinylbenzyl chloride (VBC) with the (hydrofluoric acid-etched) hydrogen-terminated silicon (Si-H) microdomains to produce a micropattemed and Si-C bonded VBC monolayer. 

Such effects are likely to be general. For example, rhodium-catalyzed intramolecular C-H insertion with diazo compounds, which are tethered by alkoxyamines, afforded either 1,5- (Z=CHj) or the unusual 1,7-insertion products (Z=0, Figure 11.40). ... 

The N-terminus of peptide sequences obtained from solid phase synthesis was transformed into a carboxylic acid group by the action of glutaric anhydride. NMP initiator tethered to the N-terminus of the peptide was then introduced via reaction of the benzyUc amine of a fluorine-labeled alkoxyamine with the previously modifled peptide. The peptide-supported initiator was then used to create block copolymers, under conditions that promote sequential NMP of terf-butyl acrylate and methyl acrylate [84],... 

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