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.
| Original language | English |
|---|---|
| Article number | 12 |
| Journal | Communications Chemistry |
| Volume | 2 |
| Issue number | 1 |
| DOIs | |
| Publication status | Published - Dec 1 2019 |
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All Science Journal Classification (ASJC) codes
- Chemistry(all)
- Materials Chemistry
- Environmental Chemistry
- Biochemistry
Cite this
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.
In: Communications Chemistry, Vol. 2, No. 1, 12, 01.12.2019.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Cupric-superoxide complex that induces a catalytic aldol reaction-type C–C bond formation
AU - Abe, Tsukasa
AU - Hori, Yuta
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
N2 - 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.
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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UR - http://www.scopus.com/inward/citedby.url?scp=85064470087&partnerID=8YFLogxK
U2 - 10.1038/s42004-019-0115-6
DO - 10.1038/s42004-019-0115-6
M3 - Article
AN - SCOPUS:85064470087
VL - 2
JO - Communications Chemistry
JF - Communications Chemistry
SN - 2399-3669
IS - 1
M1 - 12
ER -