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Synfacts 2016; 12(07): 0683
DOI: 10.1055/s-0035-1562334
Synthesis of Materials and Unnatural Products
© Georg Thieme Verlag Stuttgart · New York

Doubling Down on Diamines for Direct Arylation Polymerization

Contributor(s):
Timothy M. Swager
,
John F. Fennell Jr.
Iizuka E, Wakioka M, Ozawa F * Kyoto University, Japan
Mixed-Ligand Approach to Palladium-Catalyzed Direct Arylation Polymerization: Effective Prevention of Structural Defects Using Diamines.

Macromolecules 2016;
49: 3310-3317
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Further Information

Publication History

Publication Date:
17 June 2016 (online)

 
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Key words

direct arylation - palladium catalysis - cross-coupling - co-ligands

Significance

Side reactions such as homo-coupling and C–H activation at undesirable positions lead to branching, cross-linking, and the formation of insoluble materials during direct arylation polymerization (DArP). The authors developed a novel, mixed ligand catalyst system for palladium-catalyzed DArP. With the addition of tetramethyl-ethylenediamine (TMEDA) as a co-ligand, these side reactions have been prevented and higher polymer molecular weights can be achieved.


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Comment

The presence of TMEDA as basic co-ligand interferes with a catalytic cycle that leads to aryl halide (DTS-I2) reduction and homo-coupling of an unfunctionalized arene (DTS), the so-called trans route. This promotes the desired cross-coupling reaction to form poly(DTS-alt-TPD) through the cis route.


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