Cupric-superoxide complex that induces a catalytic aldol reaction-type C–C bond formation

Tsukasa Abe, Yuta Hori, Yoshihito Shiota, Takehiro Ohta, Yuma Morimoto, Hideki Sugimoto, Takashi Ogura, Kazunari Yoshizawa, Shinobu Itoh

研究成果: ジャーナルへの寄稿記事

5 引用 (Scopus)

抄録

Much recent attention has been focused on the structure and reactivity of transition-metal superoxide complexes, among which mononuclear copper(II)-superoxide complexes are recognized as key reactive intermediates in many biological and abiological dioxygen-activation processes. So far, several types of copper(II)-superoxide complexes have been developed and their electrophilic reactivity has been explored in C–H and O–H bond activation reactions. Here we demonstrate that a mononuclear copper(II)-(end-on)superoxide complex supported by a N-[(2-pyridyl)methyl]-1,5-diazacyclooctane tridentate ligand can induce catalytic C–C bond formation reaction between carbonyl compounds (substrate) and the solvent molecule (acetone), giving β-hydroxy-ketones (aldol). Kinetic and spectroscopic studies at low temperature as well as DFT calculation studies support a nucleophilic reactivity of the superoxide species toward the carbonyl compounds, providing new insights into the reactivity of transition-metal superoxide species not only in biological oxidation reactions but also in synthetic organic chemistry.

元の言語英語
記事番号12
ジャーナルCommunications Chemistry
2
発行部数1
DOI
出版物ステータス出版済み - 12 1 2019

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Superoxides
carbonyl compound
Carbonyl compounds
transition element
copper
Copper
Transition metals
Chemical activation
ketone
acetone
Ketones
Discrete Fourier transforms
Acetone
ligand
Ligands
Organic Chemistry
oxidation
substrate
kinetics
Oxidation

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Chemistry
  • Environmental Chemistry
  • Biochemistry

これを引用

Cupric-superoxide complex that induces a catalytic aldol reaction-type C–C bond formation. / Abe, Tsukasa; Hori, Yuta; Shiota, Yoshihito; Ohta, Takehiro; Morimoto, Yuma; Sugimoto, Hideki; Ogura, Takashi; Yoshizawa, Kazunari; Itoh, Shinobu.

:: Communications Chemistry, 巻 2, 番号 1, 12, 01.12.2019.

研究成果: ジャーナルへの寄稿記事

Abe, Tsukasa ; Hori, Yuta ; Shiota, Yoshihito ; Ohta, Takehiro ; Morimoto, Yuma ; Sugimoto, Hideki ; Ogura, Takashi ; Yoshizawa, Kazunari ; Itoh, Shinobu. / Cupric-superoxide complex that induces a catalytic aldol reaction-type C–C bond formation. :: Communications Chemistry. 2019 ; 巻 2, 番号 1.
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abstract = "Much recent attention has been focused on the structure and reactivity of transition-metal superoxide complexes, among which mononuclear copper(II)-superoxide complexes are recognized as key reactive intermediates in many biological and abiological dioxygen-activation processes. So far, several types of copper(II)-superoxide complexes have been developed and their electrophilic reactivity has been explored in C–H and O–H bond activation reactions. Here we demonstrate that a mononuclear copper(II)-(end-on)superoxide complex supported by a N-[(2-pyridyl)methyl]-1,5-diazacyclooctane tridentate ligand can induce catalytic C–C bond formation reaction between carbonyl compounds (substrate) and the solvent molecule (acetone), giving β-hydroxy-ketones (aldol). Kinetic and spectroscopic studies at low temperature as well as DFT calculation studies support a nucleophilic reactivity of the superoxide species toward the carbonyl compounds, providing new insights into the reactivity of transition-metal superoxide species not only in biological oxidation reactions but also in synthetic organic chemistry.",
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AU - Shiota, Yoshihito

AU - Ohta, Takehiro

AU - Morimoto, Yuma

AU - Sugimoto, Hideki

AU - Ogura, Takashi

AU - Yoshizawa, Kazunari

AU - Itoh, Shinobu

PY - 2019/12/1

Y1 - 2019/12/1

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AB - Much recent attention has been focused on the structure and reactivity of transition-metal superoxide complexes, among which mononuclear copper(II)-superoxide complexes are recognized as key reactive intermediates in many biological and abiological dioxygen-activation processes. So far, several types of copper(II)-superoxide complexes have been developed and their electrophilic reactivity has been explored in C–H and O–H bond activation reactions. Here we demonstrate that a mononuclear copper(II)-(end-on)superoxide complex supported by a N-[(2-pyridyl)methyl]-1,5-diazacyclooctane tridentate ligand can induce catalytic C–C bond formation reaction between carbonyl compounds (substrate) and the solvent molecule (acetone), giving β-hydroxy-ketones (aldol). Kinetic and spectroscopic studies at low temperature as well as DFT calculation studies support a nucleophilic reactivity of the superoxide species toward the carbonyl compounds, providing new insights into the reactivity of transition-metal superoxide species not only in biological oxidation reactions but also in synthetic organic chemistry.

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