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Synfacts 2007(9): 0933-0933  
DOI: 10.1055/s-2007-968897
Synthesis of Materials and Unnatural Products
© Georg Thieme Verlag Stuttgart · New York

1,3-Butadiyne-Bridged Diporphyrins

Contributor(s): Timothy M. Swager, Koushik Venkatesan
I. Hisaki, S. Hiroto, K. S. Kim, S. B. Noh, D. Kim*, H. Shinokubo*, A. Osuka*
Yonsei University, Seoul, Korea and Kyoto University, Kyoto, Japan
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Publication History

Publication Date:
23 August 2007 (online)

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Significance

The authors report the synthesis of doubly β-to-β butadiyne-bridged diporphyrins and their interesting two-photon-absorption (TPA) properties. Diporphyrins were prepared from β-borylated porphyrins. Treatment of mono- and diboryl porphyrins with oxone in a THF/acetone/water suspension successfully gave the corresponding mono- and dihydroxyporphyrins. The trifluoromethanesulfonyl derivatives were prepared in DMF by reaction with PhNTf2 and Cs2CO3, followed by metallation with Zn(OAc)2. Installation of ethynyl groups was conducted through standard Sonogashira coupling with trimethylsilyl­acetylene followed by desilylation to provide the free alkynes in good yields. A Cu(II)-mediated oxidative coupling furnished the corresponding butadiyne-bridged porphyrin dimers.