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
N1 - Funding Information:
The present research work was financially supported by the JST-CREST (JPMJCR16P1) and a Grant-in-Aid for challenging Exploratory Research (# 16K13963) from JSPS. This work was also supported by Grant-in-Aid (# JP15K13710 and JP17H03117) from JSPS and MEXT and by the MEXT Projects of “Integrated Research Consortium on Chemical Sciences”, “Elements Strategy Initiative to Form Core Research Center”, and “Network Joint Research Center for Materials and Devices”. The computational study was mainly carried out using the computer facilities at Research Institute for Information Technology, Kyushu University.
Publisher Copyright:
© 2019, The Author(s).
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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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 -