Selective monoallylation of anilines to <i>N</i>-allyl anilines using reusable zirconium dioxide supported tungsten oxide solid catalyst

Kon, Yoshihiro; Tsurumi, Shota; Yamada, Shunsuke; Yokoi, Toshiyuki; Fujitani, Tadahiro

doi:10.1039/d2ra00198e

Cited by 2 publications

(1 citation statement)

References 52 publications

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“…The addition of La(OTf) 3 to a homogeneous Pd catalyst system is also effective for improving catalytic activity . Although various reports on the N -allylation of allylic alcohols have been published since then, − heterogeneous catalysts that can be easily separated from the reaction mixture have all required high reaction temperatures of around 100 °C. − …”

Section: Introductionmentioning

confidence: 99%

Low-Temperature N-Allylation of Allylic Alcohols via Synergistic Pd/Cu Catalysis: A Silica-Supported Dual-Metal-Complex Strategy

Sakai,

Hasegawa,

Ding

et al. 2024

ACS Catal.

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N-allylation is an important method for constructing C−N bonds in fine chemical synthesis. Accumulation of catalytically active species on the same support surface is a promising approach for achieving high catalytic efficiency. In this study, we developed a catalyst comprising Pd and Cu complexes immobilized on a silica surface. The dual-metal-complex catalyst catalyzed the N-allylation of aniline using allyl alcohol at the low temperature of 30 °C with tunable selectivity toward mono-and disubstituted products. The coimmobilization of a Cu complex increased the turnover number of the Pd complex 5.3 times, which was much higher than those of reported heterogeneous catalysts used at reaction temperatures higher than 100 °C. A wide substrate scope, recyclability, and suppression of aggregation and leaching were also confirmed. Whereas synergy was scarcely observed for the simple mixture of homogeneous Pd and Cu complexes, the dual-complex catalyst exhibited significant synergy, indicating concerted catalysis on the solid surface. Spectroscopic analysis, including XAFS, in situ IR, and DNP-enhanced 15 N NMR, and density functional theory calculations indicated that an aniline molecule is activated by the Cu complex, resulting in the efficient nucleophilic attack to a π-allylpalladium intermediate.

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Section: Introductionmentioning

confidence: 99%

Low-Temperature N-Allylation of Allylic Alcohols via Synergistic Pd/Cu Catalysis: A Silica-Supported Dual-Metal-Complex Strategy

Sakai,

Hasegawa,

Ding

et al. 2024

ACS Catal.

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Selective oxidation of benzyl alcohols by silica‐supported heterogeneous catalyst containing dioxidotungsten(VI) core

Heydari

Bikas

Shaterian

et al. 2022

Applied Organom Chemis

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A dioxidotungsten(VI) complex, [WO 2 L(CH 3 OH)]Á0.5(CH 3 OH) (1), was prepared by the reaction of WCl 6 and tridentate ONO-donor Schiff base ligand (H 2 L) that was obtained from the reaction of 2-hydroxy-1-naphthaldehyde with 4-aminobenzoic hydrazide. Both H 2 L and 1 were characterized by various analyses including nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR) and UV-Vis spectroscopy, and elemental analysis. Single crystal X-ray analysis was used to determine the crystal structure of the complex, which revealed that there is a free -NH 2 group in its structure.

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Selective monoallylation of anilines to N-allyl anilines using reusable zirconium dioxide supported tungsten oxide solid catalyst

Abstract: We present a 10 wt% WO3/ZrO2 catalyzed monoallylation reaction of anilines to give various N-allyl anilines in good yields. The developed catalytic reaction is applicable to the continuous flow synthesis of N-allyl aniline with 97% selectivity.

Cited by 2 publications

References 52 publications

Low-Temperature N-Allylation of Allylic Alcohols via Synergistic Pd/Cu Catalysis: A Silica-Supported Dual-Metal-Complex Strategy

Low-Temperature N-Allylation of Allylic Alcohols via Synergistic Pd/Cu Catalysis: A Silica-Supported Dual-Metal-Complex Strategy

Selective oxidation of benzyl alcohols by silica‐supported heterogeneous catalyst containing dioxidotungsten(VI) core

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