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Issue 18, 2011
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C,C-Diacetylenic phosphaalkenes in palladium-catalyzed cross-coupling reactions

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Abstract

The reactivity of bis-TMS-substituted C,C-diacetylenic phosphaalkene (A2PA) 1 in Sonogashira–Hagihara cross-coupling reactions has been examined. The selective and successive deprotection of the two silyl groups in 1 is enabled by the steric bulk of the Mes* group which renders the acetylenetrans to Mes* more reactive and thereby facilitates selective and consecutive couplings with iodoarenes. In situ transformation of the TMS-protected acetylenes into Cu(I)acetylides is the key step in the synthetic sequence and enables the preparation of the first dimeric A2PA linked by a phenylene spacer. cis–transIsomerization across the P[double bond, length as m-dash]C bond is triggered by a tertiary amine and exclusively observed in the case of nitrophenyl-substituted A2PAs. The introduced aryl groups are integral parts of the entire π-system as evidenced by spectroscopic and electrochemical studies.

Graphical abstract: C,C-Diacetylenic phosphaalkenes in palladium-catalyzed cross-coupling reactions

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Publication details

The article was received on 04 May 2011, accepted on 02 Jun 2011 and first published on 27 Jul 2011


Article type: Paper
DOI: 10.1039/C1OB05705G
Org. Biomol. Chem., 2011,9, 6246-6255

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    C,C-Diacetylenic phosphaalkenes in palladium-catalyzed cross-coupling reactions

    E. Öberg, X. Geng, M. Santoni and S. Ott, Org. Biomol. Chem., 2011, 9, 6246
    DOI: 10.1039/C1OB05705G

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