4.5 Article

Half-sandwich complexes of group 9 metals with N,N′-ligands for CF3 -carbenoid alkylation of N-(pyrimidin-2-yl)indole

Journal

JOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume 946-947, Issue -, Pages -

Publisher

ELSEVIER SCIENCE SA
DOI: 10.1016/j.jorganchem.2021.121899

Keywords

C-H activation; Diazo compounds; Fluorine; Indoles; Homogeneous catalysis

Funding

  1. Russian Science Foundation [17-73-30036]
  2. Ministry of Science and Higher Education of the Russian Federation

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Novel Rh and Ir complexes were synthesized and their structures were determined by X-ray diffraction. The compounds prepared, as well as related derivatives, efficiently catalyze the alkylation of N-(pyrimidin-2-yl)indole with methyl 3,3,3-trifluoro-2-diazopropionate.
The complexes [CpM(N,N'-ligand)Br]PF6 (M = Rh, Ir; N,N'-ligand = 2,2'-bipyridyl, 1,10-phenanthroline) were synthesized by reactions of bromides [CpMBr2]n with 2,2'-bipyridyl or 1,10-phenanthroline followed by a counterion exchange. The replacement of cyclooctadiene in [CpIr(cod)I]I-3 with N,N'-ligands leads to complexes [CpIr(N,N'-ligand)I]I-3 (N,N'-ligand = 2,2'-bipyridyl, 1,10-phenanthroline). The structures of [CpRh(2,2'-bipyridyl)Br]PF6, [CpIr(2,2'-bipyridyl)I]I-3, and [CpIr(1,10-phenanthroline)Br]PF6 were determined by X-ray diffraction. The compounds prepared as well as the related the tris(pyrazolyl)borate derivatives [CpCoTp]PF6 and [Cp*MTp]PF6 (M = Rh, Ir) efficiently catalyze the alkylation of N-(pyrimidin-2-yl)indole with methyl 3,3,3-trifluoro-2-diazopropionate to selectively introduce the CF3 and carboxylate functions at the C3 position of the indole moiety. In contrast, the tris(pyrazolyl)borate cobalt complex [Cp*CoTp]PF6 predominantly provides the alkylation at the C2 position. (C) 2021 Elsevier B.V. All rights reserved.

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