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. 2013 Jul 8;69(27-28):5732-5736.
doi: 10.1016/j.tet.2013.03.085.

Development of a palladium-catalyzed decarboxylative cross-coupling of (2-azaaryl)carboxylates with aryl halides

Christopher K Haley  1 , Christopher D Gilmore, Brian M Stoltz
Affiliations

Development of a palladium-catalyzed decarboxylative cross-coupling of (2-azaaryl)carboxylates with aryl halides

Christopher K Haley et al. Tetrahedron. .

Abstract

A catalytic method for the decarboxylative coupling of 2-(azaaryl)carboxylates with aryl halides is described. The decarboxylative cross-coupling presented is mediated by a system catalytic in both palladium and copper without requiring stoichiometric amounts of organometallic reagents or organoboronic acids. This method circumvents additional synthetic steps required to prepare 2-azaaryl organometallics and organoborates as nucleophilic coupling partners, which are prone to protodemetallation and protodeborylation and produce potentially toxic byproducts.

Keywords: (2-azaaryl)carboxylates; Copper; Decarboxylative cross-coupling; Palladium.

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Figures

Fig. 1
Fig. 1
The importance of 2-substituted pyridines.
Fig. 2
Fig. 2
The decarboxylative olefination and cross-coupling of aryl carboxylates.
Fig. 3
Fig. 3
Proposed mechanism of the decarboxylative cross-coupling of picolinic acid with aryl halides.
Fig. 4
Fig. 4
The decarboxylative cross-coupling of picolinic acid with aryl halides. Conditions: 0.464 mmol 14, 0.928 mmol 6, CuO2 (5 mol %), PdI2 (5 mol %), PPh3 (15 mol %), pyridine (30 mol %), 0.5 mL NMP
See this image and copyright information in PMC

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