From Polynorbornene to the Complementary Polynorbornene by Replication

Abstract

Bei einer DNA‐artigen Replikation fungiert das einzelsträngige Polynorbornen als Templat für die Adhäsion von Norbornenmonomeren über Esterbindungen (siehe Schema). Die Polymerisation der anhaftenden Monomere liefert das entsprechende unsymmetrische doppelsträngige Polymer, aus dem durch Hydrolyse eine komplementäre Polynorbornencarbonsäure erhalten wird. Bei diesem Prozess wird Information vom Templatpolymer auf das Tochterpolymer übertragen.

Unsymmetrical Polymeric Ladderphanes by Sequential Polymerization: A New Approach for the Template Synthesis of Polymers with Well‐Defined Chain Length and Narrow Polydispersity

“…There is burgeoning interest in the design and synthesis of double‐stranded (ds) polymers mimicking DNA chemistry 1–9. Most approaches towards unsymmetrical double‐stranded scaffolds are based on the independent syntheses of two complementary strands, which can then furnish the double‐helical motif through hydrogen bonding 7.…”

“…The relatively rigid backbone of polynorbornenes, such as those in 5 and 6 , offers a supporting framework for the pending groups coherently aligned towards the same direction 5. 9, 12 In addition, the presence of endo ‐ N ‐aryl‐pyrrolidene‐fused moieties in these polymers is crucial for the stereoselective formation of the comb‐like polymers with isotactic stereochemistry and essentially all double bonds in the trans configuration when 3 is used as the catalyst 12. Replication of a polynorbornene that leads to a daughter polynorbornene has thus briefly been explored, and the unsymmetrical double‐stranded polybisnorbornene 4 is obtained as the intermediate 9.…”

“…9, 12 In addition, the presence of endo ‐ N ‐aryl‐pyrrolidene‐fused moieties in these polymers is crucial for the stereoselective formation of the comb‐like polymers with isotactic stereochemistry and essentially all double bonds in the trans configuration when 3 is used as the catalyst 12. Replication of a polynorbornene that leads to a daughter polynorbornene has thus briefly been explored, and the unsymmetrical double‐stranded polybisnorbornene 4 is obtained as the intermediate 9. 13 It is envisaged that an unsymmetrical double‐stranded polymer may be formed from sequential polymerizations of a monomer containing two different polymerizable groups, which can undergo polymerization under different reaction conditions.…”

Templated Polymerization of Nucleobase Complexes via Molecular Recognition

“…Nucleobase‐templated polymerization have received intense attention in constructing nucleobase‐containing polymeric structures. [ 4–10 ] Sleiman et al. [ 4 ] reported the construction of a thymine‐containing block copolymer using nucleobase recognition to read and efficiently copy the controlled chain lengths and narrow molecular weights.…”

“…Luh et al. [ 10 ] reported the use of a polynorbornene derivative as a template to exhibit replication ability for the formation of a complementary polymer. This process has been shown to involve an unsymmetrical double‐stranded polymer.…”