Redox active dendronized polystyrenes equipped with peripheral triarylamines

Abstract

SummaryDendronized polystyrene having peripheral bromo groups was prepared from the dendronization of unfunctionalized polystyrene with dendritic diarylcarbenium ions bearing peripheral bromo groups using the “cation pool” method. The palladium-catalyzed amination of the peripheral bromo groups with diarylamine gave dendronized polystyrene equipped with peripheral triarylamines, which exhibited two sets of reversible redox peaks in the cyclic voltammetry curves.

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

“…Generation of the diarylcarbenium cation pool could be facilitated with silane electroaxuiliaries—this strategy also allowed the synthesis of dendritic molecules through iterative cation pool formation and nucleophile trapping (Figure 17J). 290–293 Yoshida reported that diaryl carbenium cations may be trapped with DMSO; the resulting sulfonium can be treated with a base to furnish the ketone, much akin to a Swern oxidation (Figure 17K). 294 An in situ protocol was also reported wherein the oxidation of an arene is carried out in the presence of DMSO.…”

Electrogenerated Cationic Reactive Intermediates: The Pool Method and Further Advances

“…The use of the dendritic diarylcarbenium ions having peripheral bromo groups enables the synthesis of dendronized polymers having peripheral redox functionalities. 107 Dendritic diarylcarbenium ion pools serve as initiators of cationic polymerizations of vinyl ethers using flow microreactor systems to give dendritic−linear (D−L) polymers (Scheme 45). 108 The carbocationic polymer growth end can be effectively trapped by various nucleophiles such as allylsilanes and ketene silyl acetals to give polymers with very narrow molecular weight distributions.…”

Polymerization of vinyl ethers initiated by dendritic cations using flow microreactors

“…Bu 4 NBF 4 was dried at 25 C/1 mmHg for 12 h. 1 was prepared according to reported procedure. 18 Unless otherwise noted, all materials were obtained from commercial suppliers and were used without further purification. All solutions used for flow reactions were prepared under the argon atmosphere using dry solvents.…”