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DOI: 10.1055/a-2193-4804
Benzoxazole or Benzothiazole as an Innate Directing Group for Palladium- and Ruthenium-Catalyzed Complementary C–H Arylation: Functionalization of Biorelevant Heterocyclic Scaffolds
M.M., S.S., L.S., and F.R.P. thank the Department of Pharmaceuticals, Ministry of Chemicals and Fertilizers, Govt. of India for their fellowships.
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Abstract
The benzoxazole and benzothiazole moieties were used as innate directing groups for Pd(II)- and Ru(II)-catalyzed C–H arylation of the biorelevant heterocycles 2-arylbenzoxazole and 2-arylbenzothiazole with diverse iodoarenes; palladium and ruthenium catalysis could be used complementarily. The use of σ-donor ligands, such as N,N-dimethylacetamide in the Pd(II) catalytic cycle, and σ-donor/π-acceptor ligands, such as PPh3 in the Ru(II) catalytic cycle, enhanced the arylation rate significantly and was governed by the C–H acidity of the C2-aryl ring of the 2-arylbenzoxazole or 2-arylbenzothiazole. These approaches have a broad substrate scope with respect to coupling partners, to accommodate electron-neutral, electron-rich, as well as electron-deficient iodoarenes; the C2-aryl unit of the 2-arylbenzoxazole or 2-arylbenzothiazole exhibited a high degree of site selectivity at the ortho C–H position, affording only monoarylated derivatives in decent yields; the reactions are functional-group-tolerant and applicable to gram-scale production.
Key words
innate/native directing group - palladium catalysis - ruthenium catalysis - complementary C–H activation - monoarylation - biosignificant scaffolds - site selectivitySupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2193-4804.
- Supporting Information
Publication History
Received: 06 September 2023
Accepted after revision: 17 October 2023
Accepted Manuscript online:
17 October 2023
Article published online:
13 November 2023
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