6 research outputs found

    Asymmetric Friedel–Crafts-Type Reaction of 2‑Vinylindoles to <i>N</i>‑Boc Imines Using a Chiral Imidazolidine-Containing NCN-Pincer Pd Catalyst

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    A chiral imidazolidine-containing NCN-pincer Pd-OTf complex (NCN-Pd cat) promoted the asymmetric nucleophilic addition of unprotected 2-vinylindoles to N-Boc imines in a Friedel–Crafts-type manner. The chiral (2-vinyl-1H-indol-3-yl)methanamine products become nice platforms for constructing multiple ring systems

    Metallaantiaromaticity of 10-Platinacorrole Complexes

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    The aromaticity of cyclic π-conjugated organometallic compounds is known as metallaaromaticity. π-Conjugated metallacycles, such as metallabenzenes and metallapentalenes, have been investigated in order to understand the involvement of the d electrons from the metal center in the π-conjugated systems of the organic ligands. Here, we report the synthesis of Pd­(II) 10-platinacorrole complexes with cyclooctadiene (COD) and norbornadiene (NBD) ligands. While the Pd­(II) 10-platinacorrole COD complex adopts a distorted structure without showing appreciable antiaromaticity, the corresponding NBD complex exhibits a distinct antiaromatic character due to its highly planar conformation. Detailed density functional theory (DFT) calculations revealed that two d orbitals are involved in macrocyclic π-conjugation. We furthermore demonstrated that Craig–Möbius antiaromaticity is not present in the studied system. The synthesis of 10-platinacorroles enables a systematic comparison of the antiaromaticity and aromaticity of closely related porphyrin analogues, providing a better understanding of π-conjugation that involves d orbitals
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