Aromatic Amine Catalysts for the O₂-Mediated Cross-Dehydrogenative Phenothiazination Reaction?

Abstract

Metal-free aromatic amines have been utilized recently as redox-active catalysts in various oxidative coupling reactions. In this study, we investigated a series of aromatic amines and their potential redox catalytic activity, in particular compared to our previously reported amino-Te(II) catalysts. The O₂-mediated cross-dehydrogenative phenothiazination of phenols was utilized as a benchmark test reaction, as well as the O₂-mediated cross-dehydrogenative coupling of indoles. We thus identified a proton sponge as an effective aromatic amine redox catalyst. It was moreover found that although the proton sponge displays clear catalytic activity, it is generally less active than previously reported phenotellurazine catalysts. The insights provided by this study should guide future research efforts for the development of innovative redox-catalyzed cross-dehydrogenative coupling reactions.

Key words

redox catalysis - proton sponge - amine catalysis - tellurium catalysis - O₂ activation - cross-dehydrogenative coupling

Publication History

Received: 04 September 2023

Accepted after revision: 11 December 2023

Accepted Manuscript online:
11 December 2023

Article published online:
09 February 2024

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• 57 General Procedure Phenothiazine (0.5 mmol, 1 equiv.), phenol (1.5 mmol, 3 equiv.), K₂HPO₄ (87 mg, 0.5 mmol, 1 equiv.), and proton sponge cat14 (10.87 mg, 0.05 mmol, 10 mol%) are dissolved in p-xylene (1 mL) in a closed 10 mL vial, and O₂ is bubbled through the solution for about 2 min. The reaction mixture is stirred for 3 h at 130 °C. The crude product is purified directly by flash column chromatography yielding the title compound. (For the scale-up experiment at 2 mmol phenothiazine, the reactor vial was 20 mL).