Synthesis 2008(14): 2257-2263  
DOI: 10.1055/s-2008-1078450
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Regioselective Cobalt-Catalyzed Diels-Alder Reaction towards 1,3-Disubstituted and 1,2,3-Trisubstituted Benzene Derivatives

Gerhard Hilt*, Michael Danz
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein Straße, 35043 Marburg, Germany
Fax: +49(6421)2825677; e-Mail: [email protected];
Further Information

Publication History

Received 7 March 2008
Publication Date:
11 June 2008 (online)

Abstract

A straightforward reaction sequence consisting of the Wittig olefination of aldehydes utilizing allyltriphenylphosphonium bromide for the generation of 1-substituted 1,3-dienes, cobalt-catalyzed neutral Diels-Alder reaction with terminal and internal alkynes, and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) oxidation of the dihydroaromatic intermediates leads to regiochemically enriched biphenyl, terphenyl, and silyl-functionalized benzene derivatives in good to excellent yields. Starting from a 1,3-diyne and a 1,3-diene, the reaction sequence consisting of cobalt-catalyzed Diels-Alder reaction, DDQ oxidation, and cobalt-catalyzed cyclotrimerization with acetylene gave an axially chiral biphenyl-terphenyl product.

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