Suzuki–Miyaura cross-coupling reaction on copper-trans-A2B corroles with excellent functional group tolerance

The palladium-catalyzed Suzuki–Miyaura cross-coupling reaction has been investigated on meso-substituted trans-A2B-corrole using tailored Pd-catalyst systems. We present the first examples of Suzuki–Miyaura cross-coupling reactions on meso-substituted trans-A2B-corrole derivatives with neutral, ster...

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Veröffentlicht in:Tetrahedron 2011-06, Vol.67 (23), p.4243-4252
Hauptverfasser: König, Michael, Reith, Lorenz Michael, Monkowius, Uwe, Knör, Günther, Bretterbauer, Klaus, Schoefberger, Wolfgang
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Sprache:eng
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Zusammenfassung:The palladium-catalyzed Suzuki–Miyaura cross-coupling reaction has been investigated on meso-substituted trans-A2B-corrole using tailored Pd-catalyst systems. We present the first examples of Suzuki–Miyaura cross-coupling reactions on meso-substituted trans-A2B-corrole derivatives with neutral, sterically hindered, inactivated and heteroaromatic boronic acids and esters, alkenylboronic acids, as well as quickly deboronating aryl boronic acids and benzo-condensated five membered heterocyclic boronic acids. In addition, we established a high-yield procedure for the Suzuki–Miyaura cross-coupling reaction of corroles with neutral boronic acids. Due to the lability of the free-base corrole macrocycles, functionalization of the corrole periphery was performed with the corresponding Cu-metallated species. meso-Substituted trans-A2B-corrole can hence be regarded as highly versatile platform towards more sophisticated corrole systems. X-ray structure analysis of a functionalized meso-substituted trans-A2B copper corrole exhibited the typical features of such a Cu-complex: short N–Cu distances and a saddled corrole configuration. Moreover, we observed a sensitivity of the formal oxidation state of the coordinated copper ions towards Suzuki–Miyaura cross-coupling reaction conditions, where the central copper(III) ion approaches the characteristic features of a copper(II) species. This redox behaviour was examined by UV/vis absorption spectra, nuclear magnetic resonance (NMR) experiments and time-dependent density functional theoretical calculations. [Display omitted]
ISSN:0040-4020
1464-5416
DOI:10.1016/j.tet.2011.04.024