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Aerobic oxidative Heck/dehydrogenation reactions of cyclohexenones: efficient access to meta-substituted phenols.

ABSTRACT:

SUBMITTER: Izawa Y

PROVIDER: S-EPMC3634920 | biostudies-literature | 2013 Mar

REPOSITORIES: biostudies-literature

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Aerobic oxidative Heck/dehydrogenation reactions of cyclohexenones: efficient access to meta-substituted phenols.

Izawa Yusuke Y Zheng Changwu C Stahl Shannon S SS

Angewandte Chemie (International ed. in English) 20130219 13

PMID: 23423740

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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.

Dataset Information

Aerobic oxidative Heck/dehydrogenation reactions of cyclohexenones: efficient access to meta-substituted phenols.

Publications

Aerobic oxidative Heck/dehydrogenation reactions of cyclohexenones: efficient access to meta-substituted phenols.

Similar Datasets

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