Polyethyleneimine-Modified Polymer as an Efficient Palladium Scavenger and Effective Catalyst Support for a Functional Heterogeneous Palladium Catalyst

Tsuyoshi Yamada; Yutaka Kobayashi; Naoya Ito; Tomohiro Ichikawa; Kwihwan Park; Kouki Kunishima; Shun Ueda; Masahiro Mizuno; Tadashi Adachi; Yoshinari Sawama; Yasunari Monguchi; Hironao Sajiki

doi:10.1021/acsomega.9b00707

Polyethyleneimine-Modified Polymer as an Efficient Palladium Scavenger and Effective Catalyst Support for a Functional Heterogeneous Palladium Catalyst

Tsuyoshi Yamada, Yutaka Kobayashi, Naoya Ito, Tomohiro Ichikawa, Kwihwan Park, Kouki Kunishima, Shun Ueda, Masahiro Mizuno, Tadashi Adachi, Yoshinari Sawama, Yasunari Monguchi, Hironao Sajiki^*

^*Corresponding author for this work

Synthetic and Medicinal Chemistry

Research output: Contribution to journal › Article › peer-review

22 Scopus citations

Abstract

The polyethyleneimine-modified polymers, polystyrene-divinylbenzene-based (TAs) and polymethacrylate-based polymers (TAm), were used as palladium scavengers to eliminate residual palladium species after palladium on carbon-catalyzed Sonogashira-type coupling reaction. Since both TAs and TAm indicated relatively favorable elimination abilities toward residual palladium species in the reaction mixture, the affinities of TAs and TAm for palladium species were used as supports for palladium catalysts. The TAm-supported palladium catalyst (Pd/TAm) indicated better catalyst properties for the chemoselective hydrogenation compared to those of the corresponding TAs-supported palladium catalyst (Pd/TAs). Aromatic benzyl ethers; aromatic and aliphatic N-Cbzs; and aromatic carbonyl groups were smoothly hydrogenated in the presence of 1-5 mol % of Pd/TAm in MeOH or 2-PrOH. In contrast, the hydrogenation of aromatic ketones was selectively suppressed in morpholine which act as appropriate catalyst poison and solvent. Furthermore, Pd/TAm-catalyzed chemoselective hydrogenation was applicable to continuous-flow reaction.

Original language	English
Pages (from-to)	10243-10251
Number of pages	9
Journal	ACS Omega
Volume	4
Issue number	6
DOIs	https://doi.org/10.1021/acsomega.9b00707
State	Published - 2019/06/13

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering

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Yamada, T., Kobayashi, Y., Ito, N., Ichikawa, T., Park, K., Kunishima, K., Ueda, S., Mizuno, M., Adachi, T., Sawama, Y., Monguchi, Y., & Sajiki, H. (2019). Polyethyleneimine-Modified Polymer as an Efficient Palladium Scavenger and Effective Catalyst Support for a Functional Heterogeneous Palladium Catalyst. ACS Omega, 4(6), 10243-10251. https://doi.org/10.1021/acsomega.9b00707

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title = "Polyethyleneimine-Modified Polymer as an Efficient Palladium Scavenger and Effective Catalyst Support for a Functional Heterogeneous Palladium Catalyst",

abstract = "The polyethyleneimine-modified polymers, polystyrene-divinylbenzene-based (TAs) and polymethacrylate-based polymers (TAm), were used as palladium scavengers to eliminate residual palladium species after palladium on carbon-catalyzed Sonogashira-type coupling reaction. Since both TAs and TAm indicated relatively favorable elimination abilities toward residual palladium species in the reaction mixture, the affinities of TAs and TAm for palladium species were used as supports for palladium catalysts. The TAm-supported palladium catalyst (Pd/TAm) indicated better catalyst properties for the chemoselective hydrogenation compared to those of the corresponding TAs-supported palladium catalyst (Pd/TAs). Aromatic benzyl ethers; aromatic and aliphatic N-Cbzs; and aromatic carbonyl groups were smoothly hydrogenated in the presence of 1-5 mol % of Pd/TAm in MeOH or 2-PrOH. In contrast, the hydrogenation of aromatic ketones was selectively suppressed in morpholine which act as appropriate catalyst poison and solvent. Furthermore, Pd/TAm-catalyzed chemoselective hydrogenation was applicable to continuous-flow reaction.",

author = "Tsuyoshi Yamada and Yutaka Kobayashi and Naoya Ito and Tomohiro Ichikawa and Kwihwan Park and Kouki Kunishima and Shun Ueda and Masahiro Mizuno and Tadashi Adachi and Yoshinari Sawama and Yasunari Monguchi and Hironao Sajiki",

note = "Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

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doi = "10.1021/acsomega.9b00707",

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Yamada, T, Kobayashi, Y, Ito, N, Ichikawa, T, Park, K, Kunishima, K, Ueda, S, Mizuno, M, Adachi, T, Sawama, Y, Monguchi, Y & Sajiki, H 2019, 'Polyethyleneimine-Modified Polymer as an Efficient Palladium Scavenger and Effective Catalyst Support for a Functional Heterogeneous Palladium Catalyst', ACS Omega, vol. 4, no. 6, pp. 10243-10251. https://doi.org/10.1021/acsomega.9b00707

TY - JOUR

T1 - Polyethyleneimine-Modified Polymer as an Efficient Palladium Scavenger and Effective Catalyst Support for a Functional Heterogeneous Palladium Catalyst

AU - Yamada, Tsuyoshi

AU - Kobayashi, Yutaka

AU - Ito, Naoya

AU - Ichikawa, Tomohiro

AU - Park, Kwihwan

AU - Kunishima, Kouki

AU - Ueda, Shun

AU - Mizuno, Masahiro

AU - Adachi, Tadashi

AU - Sawama, Yoshinari

AU - Monguchi, Yasunari

AU - Sajiki, Hironao

PY - 2019/6/13

Y1 - 2019/6/13

N2 - The polyethyleneimine-modified polymers, polystyrene-divinylbenzene-based (TAs) and polymethacrylate-based polymers (TAm), were used as palladium scavengers to eliminate residual palladium species after palladium on carbon-catalyzed Sonogashira-type coupling reaction. Since both TAs and TAm indicated relatively favorable elimination abilities toward residual palladium species in the reaction mixture, the affinities of TAs and TAm for palladium species were used as supports for palladium catalysts. The TAm-supported palladium catalyst (Pd/TAm) indicated better catalyst properties for the chemoselective hydrogenation compared to those of the corresponding TAs-supported palladium catalyst (Pd/TAs). Aromatic benzyl ethers; aromatic and aliphatic N-Cbzs; and aromatic carbonyl groups were smoothly hydrogenated in the presence of 1-5 mol % of Pd/TAm in MeOH or 2-PrOH. In contrast, the hydrogenation of aromatic ketones was selectively suppressed in morpholine which act as appropriate catalyst poison and solvent. Furthermore, Pd/TAm-catalyzed chemoselective hydrogenation was applicable to continuous-flow reaction.

AB - The polyethyleneimine-modified polymers, polystyrene-divinylbenzene-based (TAs) and polymethacrylate-based polymers (TAm), were used as palladium scavengers to eliminate residual palladium species after palladium on carbon-catalyzed Sonogashira-type coupling reaction. Since both TAs and TAm indicated relatively favorable elimination abilities toward residual palladium species in the reaction mixture, the affinities of TAs and TAm for palladium species were used as supports for palladium catalysts. The TAm-supported palladium catalyst (Pd/TAm) indicated better catalyst properties for the chemoselective hydrogenation compared to those of the corresponding TAs-supported palladium catalyst (Pd/TAs). Aromatic benzyl ethers; aromatic and aliphatic N-Cbzs; and aromatic carbonyl groups were smoothly hydrogenated in the presence of 1-5 mol % of Pd/TAm in MeOH or 2-PrOH. In contrast, the hydrogenation of aromatic ketones was selectively suppressed in morpholine which act as appropriate catalyst poison and solvent. Furthermore, Pd/TAm-catalyzed chemoselective hydrogenation was applicable to continuous-flow reaction.

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JF - ACS Omega

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ER -

Polyethyleneimine-Modified Polymer as an Efficient Palladium Scavenger and Effective Catalyst Support for a Functional Heterogeneous Palladium Catalyst

Abstract

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