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

TETRAHEDRON

卷:67

Article

Koenig, Michael¹  Reith, Lorenz Michael¹  Monkowius, Uwe¹  Knoer, Guenther¹  Bretterbauer, Klaus²  Schoefberger, Wolfgang¹ 

[1] Johannes Kepler Univ Linz, Inst Inorgan Chem, A-4040 Linz, Austria

[2] Johannes Kepler Univ Linz, Inst Chem Technol Organ Subst, A-4040 Linz, Austria

关键词: Corrole;    Copper;    Suzuki-Miyaura coupling reaction;    Pd-catalysts;    Boronic acids/esters;    Density functional theory (DFT);    Time-dependent DFT;   

DOI  :  10.1016/j.tet.2011.04.024

来源: Elsevier

【 摘 要 】

The palladium-catalyzed Suzuki-Miyaura cross-coupling reaction has been investigated on meso-substituted trans-A(2)B-corrole using tailored Pd-catalyst systems. We present the first examples of Suzuki-Miyaura cross-coupling reactions on meso-substituted trans-A(2)B-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. mesa-Substituted trans-A(2)B-corrole can hence be regarded as highly versatile platform towards more sophisticated corrole systems. X-ray structure analysis of a functionalized meso-substituted trans-A(2)B 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. (C) 2011 Elsevier Ltd. All rights reserved.

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