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Multicomponent synthesis via acceptorless alcohol dehydrogenation: an easy access to tri-substituted pyridines.

ABSTRACT: Herein, we report palladium supported on a hydroxyapatite catalyst for synthesizing tri-substituted pyridines using ammonium acetate as the nitrogen source via acceptorless alcohol dehydrogenation strategy. The strategy offers a broad substrate scope using inexpensive and readily available alcohols as the starting material. The catalyst was prepared using a simple method and analyzed by several techniques, including FE-SEM, EDS, HR-TEM, BET, XRD, FT-IR, UV-visible spectroscopy, and XPS, demonstrating the anchoring of Pd nanoparticles on hydroxyapatite in the zero oxidation state. Moreover, several controlled experiments were carried out to understand the reaction pathway and a suitable mechanism has been proposed.

SUBMITTER: P H

PROVIDER: S-EPMC10988360 | biostudies-literature | 2024 Mar

REPOSITORIES: biostudies-literature

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Multicomponent synthesis <i>via</i> acceptorless alcohol dehydrogenation: an easy access to tri-substituted pyridines.

P Hima H M Vageesh V Dey Raju R

RSC advances 20240301 15

Herein, we report palladium supported on a hydroxyapatite catalyst for synthesizing tri-substituted pyridines using ammonium acetate as the nitrogen source <i>via</i> acceptorless alcohol dehydrogenation strategy. The strategy offers a broad substrate scope using inexpensive and readily available alcohols as the starting material. The catalyst was prepared using a simple method and analyzed by several techniques, including FE-SEM, EDS, HR-TEM, BET, XRD, FT-IR, UV-visible spectroscopy, and XPS, d ...[more]

PMID: 38572342

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Project description:The non-oxidative catalytic dehydrogenation of light alkanes via C-H activation is a highly endothermic process that generally requires high temperatures and/or a sacrificial hydrogen acceptor to overcome unfavorable thermodynamics. This is complicated by alkanes being such poor ligands, meaning that binding at metal centers prior to C-H activation is disfavored. We demonstrate that by biasing the pre-equilibrium of alkane binding, by using solid-state molecular organometallic chemistry (SMOM-chem), well-defined isobutane and cyclohexane σ-complexes, [Rh(Cy2PCH2CH2PCy2)(η:η-(H3C)CH(CH3)2][BArF4] and [Rh(Cy2PCH2CH2PCy2)(η:η-C6H12)][BArF4] can be prepared by simple hydrogenation in a solid/gas single-crystal to single-crystal transformation of precursor alkene complexes. Solid-gas H/D exchange with D2 occurs at all C-H bonds in both alkane complexes, pointing to a variety of low energy fluxional processes that occur for the bound alkane ligands in the solid-state. These are probed by variable temperature solid-state nuclear magnetic resonance experiments and periodic density functional theory (DFT) calculations. These alkane σ-complexes undergo spontaneous acceptorless dehydrogenation at 298 K to reform the corresponding isobutene and cyclohexadiene complexes, by simple application of vacuum or Ar-flow to remove H2. These processes can be followed temporally, and modeled using classical chemical, or Johnson-Mehl-Avrami-Kologoromov, kinetics. When per-deuteration is coupled with dehydrogenation of cyclohexane to cyclohexadiene, this allows for two successive KIEs to be determined [kH/kD = 3.6(5) and 10.8(6)], showing that the rate-determining steps involve C-H activation. Periodic DFT calculations predict overall barriers of 20.6 and 24.4 kcal/mol for the two dehydrogenation steps, in good agreement with the values determined experimentally. The calculations also identify significant C-H bond elongation in both rate-limiting transition states and suggest that the large kH/kD for the second dehydrogenation results from a pre-equilibrium involving C-H oxidative cleavage and a subsequent rate-limiting β-H transfer step.

Dataset Information

Multicomponent synthesis via acceptorless alcohol dehydrogenation: an easy access to tri-substituted pyridines.

Publications

Multicomponent synthesis <i>via</i> acceptorless alcohol dehydrogenation: an easy access to tri-substituted pyridines.

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