Recyclable and efficient polyurethane-Ir catalysts for direct borylation of aromatic compounds

Akihiro Kimura, Haruka Hayama, Jun Ya Hasegawa, Hassan Nageh, Yue Wang, Naofumi Naga, Mayumi Nishida, Tamaki Nakano

研究成果: Article

1 引用 (Scopus)

抄録

Four polyurethanes comprising 2,2′-bipyridyl moieties incorporated in the main chain were synthesized as a novel polymer ligand for the Ir(i)-catalyzed direct borylation of aromatic compounds. The polyurethanes were insoluble in common organic solvents and soluble in dimethylsulfoxide. The borylation reaction of benzene catalyzed by Ir(i) in the presence of the polymer prepared from 4,4′-bis(hydroxylmethyl)-2,2′-bipyridyl and 1,6-diisocyanatohexane led to the catalytic activities comparable to that in the presence of 2,2′-bipyridyl, while the polymers prepared by the reactions of 4,4′-bis(hydroxylmethyl)-2,2′-bipyridyl with 1,4-diisocyanatobenzene, 1,4-diisocyanato-3-methylbenzene, and bis(4-isocyanatophenyl)methane possesed lower catalytic activities. The high activity observed using the 1,6-diisocyanatohexane-based polyurethane catalyst could have a connection to the fact that this polymer has the highest tendency to form the inter-chain hydrogen bond. The borylation reaction systems with the polymers were biphasic, where the top and bottom layers contained the product and the polymer-based catalysts, respectively. Due to the phase separation, the product isolation and catalyst recycle were readily performed through a simple decantation. The catalyst prepared from 1,6-diisocyanatohexane-based polyurethane was able to be recycled at least five times without a significant decrease in activity. Further, the regio-selectivity in borylation of toluene, anisole, and trifluoromethybenzene was studied using the polyurethane ligands as well as the corresponding small-molecular ligands.

元の言語English
ページ(範囲)7406-7415
ページ数10
ジャーナルPolymer Chemistry
8
発行部数47
DOI
出版物ステータスPublished - 2017 12 21

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Polyurethanes
Aromatic compounds
2,2'-Dipyridyl
Polymers
Catalysts
Ligands
Catalyst activity
Methane
Toluene
Dimethyl Sulfoxide
Benzene
Phase separation
Organic solvents
Hydrogen bonds
1,6-hexamethylene diisocyanate

ASJC Scopus subject areas

  • Bioengineering
  • Biochemistry
  • Polymers and Plastics
  • Organic Chemistry

これを引用

Kimura, A., Hayama, H., Hasegawa, J. Y., Nageh, H., Wang, Y., Naga, N., ... Nakano, T. (2017). Recyclable and efficient polyurethane-Ir catalysts for direct borylation of aromatic compounds. Polymer Chemistry, 8(47), 7406-7415. https://doi.org/10.1039/c7py01509g

Recyclable and efficient polyurethane-Ir catalysts for direct borylation of aromatic compounds. / Kimura, Akihiro; Hayama, Haruka; Hasegawa, Jun Ya; Nageh, Hassan; Wang, Yue; Naga, Naofumi; Nishida, Mayumi; Nakano, Tamaki.

:: Polymer Chemistry, 巻 8, 番号 47, 21.12.2017, p. 7406-7415.

研究成果: Article

Kimura, A, Hayama, H, Hasegawa, JY, Nageh, H, Wang, Y, Naga, N, Nishida, M & Nakano, T 2017, 'Recyclable and efficient polyurethane-Ir catalysts for direct borylation of aromatic compounds', Polymer Chemistry, 巻. 8, 番号 47, pp. 7406-7415. https://doi.org/10.1039/c7py01509g
Kimura, Akihiro ; Hayama, Haruka ; Hasegawa, Jun Ya ; Nageh, Hassan ; Wang, Yue ; Naga, Naofumi ; Nishida, Mayumi ; Nakano, Tamaki. / Recyclable and efficient polyurethane-Ir catalysts for direct borylation of aromatic compounds. :: Polymer Chemistry. 2017 ; 巻 8, 番号 47. pp. 7406-7415.
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abstract = "Four polyurethanes comprising 2,2′-bipyridyl moieties incorporated in the main chain were synthesized as a novel polymer ligand for the Ir(i)-catalyzed direct borylation of aromatic compounds. The polyurethanes were insoluble in common organic solvents and soluble in dimethylsulfoxide. The borylation reaction of benzene catalyzed by Ir(i) in the presence of the polymer prepared from 4,4′-bis(hydroxylmethyl)-2,2′-bipyridyl and 1,6-diisocyanatohexane led to the catalytic activities comparable to that in the presence of 2,2′-bipyridyl, while the polymers prepared by the reactions of 4,4′-bis(hydroxylmethyl)-2,2′-bipyridyl with 1,4-diisocyanatobenzene, 1,4-diisocyanato-3-methylbenzene, and bis(4-isocyanatophenyl)methane possesed lower catalytic activities. The high activity observed using the 1,6-diisocyanatohexane-based polyurethane catalyst could have a connection to the fact that this polymer has the highest tendency to form the inter-chain hydrogen bond. The borylation reaction systems with the polymers were biphasic, where the top and bottom layers contained the product and the polymer-based catalysts, respectively. Due to the phase separation, the product isolation and catalyst recycle were readily performed through a simple decantation. The catalyst prepared from 1,6-diisocyanatohexane-based polyurethane was able to be recycled at least five times without a significant decrease in activity. Further, the regio-selectivity in borylation of toluene, anisole, and trifluoromethybenzene was studied using the polyurethane ligands as well as the corresponding small-molecular ligands.",
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AU - Hayama, Haruka

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AU - Naga, Naofumi

AU - Nishida, Mayumi

AU - Nakano, Tamaki

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AB - Four polyurethanes comprising 2,2′-bipyridyl moieties incorporated in the main chain were synthesized as a novel polymer ligand for the Ir(i)-catalyzed direct borylation of aromatic compounds. The polyurethanes were insoluble in common organic solvents and soluble in dimethylsulfoxide. The borylation reaction of benzene catalyzed by Ir(i) in the presence of the polymer prepared from 4,4′-bis(hydroxylmethyl)-2,2′-bipyridyl and 1,6-diisocyanatohexane led to the catalytic activities comparable to that in the presence of 2,2′-bipyridyl, while the polymers prepared by the reactions of 4,4′-bis(hydroxylmethyl)-2,2′-bipyridyl with 1,4-diisocyanatobenzene, 1,4-diisocyanato-3-methylbenzene, and bis(4-isocyanatophenyl)methane possesed lower catalytic activities. The high activity observed using the 1,6-diisocyanatohexane-based polyurethane catalyst could have a connection to the fact that this polymer has the highest tendency to form the inter-chain hydrogen bond. The borylation reaction systems with the polymers were biphasic, where the top and bottom layers contained the product and the polymer-based catalysts, respectively. Due to the phase separation, the product isolation and catalyst recycle were readily performed through a simple decantation. The catalyst prepared from 1,6-diisocyanatohexane-based polyurethane was able to be recycled at least five times without a significant decrease in activity. Further, the regio-selectivity in borylation of toluene, anisole, and trifluoromethybenzene was studied using the polyurethane ligands as well as the corresponding small-molecular ligands.

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