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Synfacts 2014; 10(8): 0809
DOI: 10.1055/s-0034-1378477
Synthesis of Materials and Unnatural Products
© Georg Thieme Verlag Stuttgart · New York

Poly(o-arylene)s from [2.2.1]Oxabicyclic Alkenes as Monomers

Contributor(s):
Timothy M. Swager
,
Byungjin Koo
Ito S, * Takahashi K, Nozaki K. * The University of Tokyo, Japan
Formal Aryne Polymerization: Use of [2.2.1]Oxabicyclic Alkenes as Aryne Equivalents.

J. Am. Chem. Soc. 2014;
136: 7547-7550
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Publication History

Publication Date:
18 July 2014 (online)

 
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Key words

poly(o-arylene)s - chain-growth polymerization - palladium

Significance

The instability of aryne has prevented its polymerization to form poly(o-arylene)s. Only few examples of oligomeric o-arylenes through iterative coupling reactions are reported. Ito, Takahashi, and Nozaki report the synthesis of poly(o-arylene)s via polymerization of [2.2.1]oxa­bicyclic alkenes, followed by acid-catalyzed de­hydration.


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Comment

In this chain-growth polymerization, the co-solvent and the additive 2,6-lutidine play key roles. Toluene may stabilize the cationic palladium catalyst species and may hinder β-oxygen elimination (the termination step). Dichloroethane (DCE) solubilizes the palladium catalyst in toluene. 2,6-Lutidine produces polymer 2 with high yields and a low polydispersity index.


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