TY - JOUR
T1 - Identification of the Optimal Framework for Nitroxyl Radical/Hydroxylamine in Copper-Cocatalyzed Aerobic Alcohol Oxidation
AU - Toda, Masaki
AU - Sasano, Yusuke
AU - Takahashi, Masaya
AU - Fujiki, Shogo
AU - Kasabata, Koki
AU - Ono, Tetsuya
AU - Sato, Katsuhiko
AU - Kashiwagi, Yoshitomo
AU - Iwabuchi, Yoshiharu
N1 - Funding Information:
This work was partially supported by JSPS KAKENHI Grant Nos. 22H02739, 21H05210 (Digitalization-driven Transformative Organic Synthesis (Digi-TOS)), and 20K06961 and by the Research Support Project for Life Science and Drug Discovery (Basis for Supporting Innovative Drug Discovery and Life Science Research (BINDS)) from AMED under Grant Number JP22ama121040.
Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/2/3
Y1 - 2023/2/3
N2 - 8-Azabicyclo[3.2.1]octan-8-ol (ABOOL) and 7-azabicyclo[2.2.1]heptan-7-ol (ABHOL) are the main homologues of hydroxylamine 2-azaadamantan-2-ol (AZADOL) and 9-azabicyclo[3.3.1]nonan-9-ol. Both homologues feature a small bicyclic backbone and are known to be stable; however, to date, they have not been used as catalysts for alcohol oxidation. Herein, we report that these hydroxylamines can efficiently catalyze the oxidation of various secondary alcohols to their corresponding ketones using molecular oxygen in ambient air as the terminal oxidant and copper cocatalysts at room temperature. Furthermore, we show that ABOOL and ABHOL can be easily synthesized from commercially available materials.
AB - 8-Azabicyclo[3.2.1]octan-8-ol (ABOOL) and 7-azabicyclo[2.2.1]heptan-7-ol (ABHOL) are the main homologues of hydroxylamine 2-azaadamantan-2-ol (AZADOL) and 9-azabicyclo[3.3.1]nonan-9-ol. Both homologues feature a small bicyclic backbone and are known to be stable; however, to date, they have not been used as catalysts for alcohol oxidation. Herein, we report that these hydroxylamines can efficiently catalyze the oxidation of various secondary alcohols to their corresponding ketones using molecular oxygen in ambient air as the terminal oxidant and copper cocatalysts at room temperature. Furthermore, we show that ABOOL and ABHOL can be easily synthesized from commercially available materials.
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U2 - 10.1021/acs.joc.2c02327
DO - 10.1021/acs.joc.2c02327
M3 - Article
AN - SCOPUS:85146533236
SN - 0022-3263
VL - 88
SP - 1434
EP - 1444
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 3
ER -