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Regioselective Haloaromatization of 1,2-Bis(ethynyl)benzene via Halogen Acids and PtCl2. Platinum-Catalyzed 6-π Electrocyclization of 1,2-Bis(1‘-haloethenyl)benzene Intermediates

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journal contribution
posted on 09.12.2005, 00:00 by Ching-Yu Lo, Manyam Praveen Kumar, Hsu-Kai Chang, Shie-Fu Lush, Rai-Shung Liu
Treatment of 1,2-bis(ethynyl)benzene (1) with aqueous HX (X = Br, I) in hot 3-pentanone (100−105 °C, 2 h) afforded 1,2-bis(1‘-haloethenyl)benzene species 2-Br and 2-I in 98% and 95% yields, respectively. The hydrochlorination of endiyne 1 failed to proceed at elevated temperature but was implemented efficiently by PtCl2 (5 mol %) in hot 3-pentanone (100 °C, 2 h) to give 1,2-bis(1‘-chloroethenyl)benzene 2-Cl in 80% yield. In the presence of PtCl2 (5 mol %), these halides 2-Cl, 2-Br, and 2-I were subsequently converted to 1-halonaphthalenes 3-Cl, 3-Br, and 3-I in the mother solution via sequential 6-π electrocyclization and dehalogenation reactions. PtCl2 (5 mol %) also effected direct haloaromatization of endiyne 1 with HX (X = Cl, Br, I) and gave 1-halonaphthalenes 3-Cl, 3-Br, and 3-I in 64−71% yields. This investigation reports the scope and the regioselectivity of haloaromatization of various enediynes catalyzed by PtCl2.