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Palladium-catalyzed aerobic dehydrogenation of substituted cyclohexanones to phenols.

ABSTRACT: Aromatic molecules are key constituents of many pharmaceuticals, electronic materials, and commodity plastics. The utility of these molecules directly reflects the identity and pattern of substituents on the aromatic ring. Here, we report a palladium(II) catalyst system, incorporating an unconventional ortho-dimethylaminopyridine ligand, for the conversion of substituted cyclohexanones to the corresponding phenols. The reaction proceeds via successive dehydrogenation of two saturated carbon-carbon bonds of the six-membered ring and uses molecular oxygen as the hydrogen acceptor. This reactivity demonstrates a versatile and efficient strategy for the synthesis of substituted aromatic molecules with fundamentally different selectivity constraints from the numerous known synthetic methods that rely on substitution of a preexisting aromatic ring.

SUBMITTER: Izawa Y

PROVIDER: S-EPMC3174491 | biostudies-literature | 2011 Jul

REPOSITORIES: biostudies-literature

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Palladium-catalyzed aerobic dehydrogenation of substituted cyclohexanones to phenols.

Izawa Yusuke Y Pun Doris D Stahl Shannon S SS

Science (New York, N.Y.) 20110609 6039

Aromatic molecules are key constituents of many pharmaceuticals, electronic materials, and commodity plastics. The utility of these molecules directly reflects the identity and pattern of substituents on the aromatic ring. Here, we report a palladium(II) catalyst system, incorporating an unconventional ortho-dimethylaminopyridine ligand, for the conversion of substituted cyclohexanones to the corresponding phenols. The reaction proceeds via successive dehydrogenation of two saturated carbon-carb ...[more]

PMID: 21659567

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Project description:Phenol, an important industrial chemical, is widely produced using the well-developed cumene process. However, demand for the development of a novel alternative method for synthesizing phenol from benzene has been increasing. Herein, we report a novel system for the synthesis of phenols through aerobic oxidative dehydrogenation of cyclohexanols and cyclohexanones, including ketone-alcohol (KA) oil, catalyzed by Mg-Al-layered double hydroxide (LDH)-supported Au-Pd alloy nanoparticles (Au-Pd/LDH). Alloying of Au and Pd and basicity of LDH are key factors in achieving the present transformation. Although monometallic Au/LDH, Pd/LDH, and their physical mixture showed almost no catalytic activity, Au-Pd/LDH exhibited markedly high catalytic activity for the dehydrogenative phenol production. Mechanistic studies showed that β-H elimination from Pd-enolate species is accelerated by Au species, likely via electronic ligand effects. Moreover, the effect of supports was critical; despite the high catalytic performance of Au-Pd/LDH, Au-Pd bimetallic nanoparticles supported on Al2O3, TiO2, MgO, and CeO2 were ineffective. Thus, the basicity of LDH plays a deterministic role in the present dehydrogenation possibly through its assistance in the deprotonation steps. The synthetic scope of the Au-Pd/LDH-catalyzed system was very broad; various substituted cyclohexanols and cyclohexanones were efficiently converted into the corresponding phenols, and N-substituted anilines were synthesized from cyclohexanones and amines. In addition, the observed catalysis was truly heterogeneous, and Au-Pd/LDH could be reused without substantial loss of its high performance. The present transformation is scalable, utilizes O2 in air as the terminal oxidant, and generates water as the only by-product, highlighting the potential practical utility and environmentally benign nature of the present transformation. Dehydrogenative aromatization of cyclohexanols proceeds through (1) oxidation of cyclohexanols to cyclohexanones; (2) dehydrogenation of cyclohexanones to cyclohexenones; and (3) disproportionation of cyclohexenones to afford the desired phenols. In the present Au-Pd/LDH-catalyzed transformation, the oxidation of the Pd-H species is included in the rate-determining step.

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Palladium-catalyzed aerobic dehydrogenation of substituted cyclohexanones to phenols.

Publications

Palladium-catalyzed aerobic dehydrogenation of substituted cyclohexanones to phenols.

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