Boron-mediated polymerization of ylides derived from allylic arsonium salts: influence of the double bond substitution on the outcome

Abstract

New oligomers or polymers are prepared by polymerization of arsonium ylides in the presence of boron compounds.

C1 polymerization: a unique tool towards polyethylene-based complex macromolecular architectures

“…The 2-substituted allylic ylides mainly lead to C3 polymerization, while terminal unsubstituted monomers result in random C1/C3 polymerization (Scheme 12). 32,33 In all cases, the polymerization involves a [1,3]-sigmatropic (or boratropic) rearrangement of the allylic boron intermediate.…”

Terpolymers from Borane‐Initiated Copolymerization of Triphenyl Arsonium and Sulfoxonium Ylides: An Unexpected Light Emission

“…The homo C3 polymer (polymer 8 , for synthesis, see our previous work, for the 1 H NMR spectrum, see the Supporting Information, Figure S16), gave an emission at 450 nm in THF solution (Figure B). Another two homopolymers (polymer 9 and 10 ) obtained by polymerization of reported allylic arsonium ylide, have similar emission behavior (Supporting Information, Figure S17). The 1 H NMR of C3 polymer 8 compared with UV irradiated one also showed a clear isomerization phenomenon (Supporting Information, Figure S18).…”

“…Later, Mioskowski et al. discovered that by using a non‐substituted allylarsonium ylide as monomer, a C1/C3 random copolymer was obtained, whereas by using terminal dimethyl substituted allylic arsonium ylide a C1 homopolymer was obtained . They explained the differences by using sigmatropic rearrangement arguments.…”

Polymethylene‐Based Copolymers by Polyhomologation or by Its Combination with Controlled/Living and Living Polymerizations

“…Dimethylsulfoxonium methylide, synthesized from trimethylsulfoxonium chloride and sodium hydride, was first used in polyhomologation with triethylborane (BEt 3 ) as initiator to produce well‐defined PMs (Scheme ) . Some substituted methylides have also been used in polyhomologation (Scheme ) . The reactivity of ylide strongly depends on the environment of the carbanion.…”