C–ON bond homolysis in alkoxyamines. Part 12: the effect of the para-substituent in the 1-phenylethyl fragment. Issue 14 (15th March 2016)

• Record Type: Journal Article
• Authors: Audran, Gérard; Brémond, Paul; Joly, Jean-Patrick; Marque, Sylvain R. A.; Yamasaki, Toshihide
• Is Part Of: Organic & biomolecular chemistry. Volume 14:Issue 14(2016)
• Page Start: 3574
• Page End: 3583
• Publication Date: 2016-03-15
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/c6ob00384b
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : The application of alkoxyamines as initiators/controllers in nitroxide mediated polymerization and as agents for theranostics requires the development of switchable (from stable one to labile one) alkoxyamines. Abstract : The application of alkoxyamines as initiators/controllers in nitroxide mediated polymerization and as agents for theranostics requires the development of switchable (from stable one to labile one) alkoxyamines. One way to achieve this is to tune the polarity of various groups carried by either the alkyl fragment or the nitroxyl fragment. Thus, the effect of protonation/deprotonation of the para -functionalized aryl moiety carried by the alkyl fragment in diethyl(2, 2-dimethyl-1-((1, 1-dimethylethyl)(1- para -subsitutedphenylethoxy)amino)propyl)phosphonate is investigated. An increase in k d is observed with increasing localized electrical effect, i.e., in the presence of electron withdrawing groups at the para position of the phenyl ring. A striking effect of the intimate ion pair on k d is also observed.