Dimerisation, rhodium complex formation and rearrangements of N-heterocyclic carbenes of indazoles

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Dimerisation, rhodium complex formation and rearrangements of N-heterocyclic carbenes of indazoles

Deprotonation of indazolium salts at low temperatures gives N-heterocyclic carbenes of indazoles (indazol-3-ylidenes) which can be trapped as rhodium complexes (X-ray analysis). In the absence of Rh, the indazol-3-ylidenes spontaneously dimerize under ring cleavage of one of the N,N-bonds and ring closure to an indazole-indole spiro compound which possesses an exocyclic imine group. The E/Z iso...

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N-Heterocyclic carbenes

The N-heterocyclic carbenes (NHC) now hold a preferredligand status in organic and organometallic chemistry. Their role in catalysis continues to grow. When the editorial staff at the Beilstein Journal of Organic Chemistry contacted me to act as a guest editor for the thematic series “N-Heterocyclic carbenes”, I was more than happy to accept what appeared to me to be a simple and exciting endea...

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Easy preparation of Cp*-functionalized N-heterocyclic carbenes and their coordination to rhodium and iridium.

A simple high-yielding method for the preparation of a tetramethylcyclopentadienyl-NHC ligand is described. This ligand has been successfully coordinated to Rh and Ir. A related Cp*-NHC ligand with a -CH(2)CMePh- linker between the Cp* and the NHC is also described, together with its coordination to Rh and Ir. This latter ligand, affords the orthocyclometallation of the phenyl ring yielding a c...

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In the investigation of efficient chemical transformations, the carbon-carbon bond-forming reactions play an outstanding role. In this context, organocatalytic processes have achieved considerable attention.1 Beside their facile reaction course, selectivity, and environmental friendliness, new synthetic strategies are made possible. Particularly, the inversion of the classical reactivity (Umpol...

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Pericyclic rearrangements of N-heterocyclic carbenes of indazole to substituted 9-aminoacridines.

On deprotonation, 1-arylindazolium salts form 1-arylindazol-3-ylidenes which rearrange spontaneously via ring cleavage, ring closure and subsequent proton transfer to substituted 9-aminoacridines. By contrast, the N-heterocyclic carbene of 2-phenylindazolium cannot rearrange similarly and was trapped by sulfur.

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ژورنال

عنوان ژورنال: Beilstein Journal of Organic Chemistry

سال: 2014

ISSN: 1860-5397

DOI: 10.3762/bjoc.10.79