Safe and Scalable Aerobic Oxidation by 2-Azaadamantan-2-ol (AZADOL)/NO                         x                          Catalysis: Large-Scale Preparation of Shi's Catalyst

Yusuke Sasano; Hikaru Sato; Shinsuke Tadokoro; Masami Kozawa; Yoshiharu Iwabuchi

doi:10.1021/acs.oprd.8b00456

Safe and Scalable Aerobic Oxidation by 2-Azaadamantan-2-ol (AZADOL)/NO _x Catalysis: Large-Scale Preparation of Shi's Catalyst

Yusuke Sasano, Hikaru Sato, Shinsuke Tadokoro, Masami Kozawa, Yoshiharu Iwabuchi

PHA - Molecular Pharmaceutical Science

Nissan Chemical Corporation

Research output: Contribution to journal › Article › peer-review

16 Citations (Scopus)

Abstract

A method for safe and scalable aerobic alcohol oxidation using 2-azaadamantan-2-ol (AZADOL), an azaadamantane-type hydroxylamine catalyst, with a NO _x cocatalyst in a conventional batch reactor has been developed. The use of 2 mol % AZADOL and 10 mol % NaNO ₂ was determined to promote aerobic alcohol oxidation quantitatively within a reasonable time (8 h). Safety is ensured by controlling the reaction temperature below the flash point of the acetic acid solvent. The robustness of the developed method is demonstrated by the 500 g scale oxidation of diacetone fructose into Shi's catalyst for asymmetric epoxidation.

Original language	English
Pages (from-to)	571-577
Number of pages	7
Journal	Organic Process Research and Development
Volume	23
Issue number	4
DOIs	https://doi.org/10.1021/acs.oprd.8b00456
Publication status	Published - 2019 Apr 19

Keywords

aerobic oxidation
alcohol oxidation
hydroxylamine
nitroxyl radical
NO
oxoammonium

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10.1021/acs.oprd.8b00456

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title = "Safe and Scalable Aerobic Oxidation by 2-Azaadamantan-2-ol (AZADOL)/NO x Catalysis: Large-Scale Preparation of Shi's Catalyst",

abstract = " A method for safe and scalable aerobic alcohol oxidation using 2-azaadamantan-2-ol (AZADOL), an azaadamantane-type hydroxylamine catalyst, with a NO x cocatalyst in a conventional batch reactor has been developed. The use of 2 mol % AZADOL and 10 mol % NaNO 2 was determined to promote aerobic alcohol oxidation quantitatively within a reasonable time (8 h). Safety is ensured by controlling the reaction temperature below the flash point of the acetic acid solvent. The robustness of the developed method is demonstrated by the 500 g scale oxidation of diacetone fructose into Shi's catalyst for asymmetric epoxidation.",

keywords = "aerobic oxidation, alcohol oxidation, hydroxylamine, nitroxyl radical, NO, oxoammonium",

author = "Yusuke Sasano and Hikaru Sato and Shinsuke Tadokoro and Masami Kozawa and Yoshiharu Iwabuchi",

note = "Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

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day = "19",

doi = "10.1021/acs.oprd.8b00456",

language = "English",

volume = "23",

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Safe and Scalable Aerobic Oxidation by 2-Azaadamantan-2-ol (AZADOL)/NO _x Catalysis: Large-Scale Preparation of Shi's Catalyst. / Sasano, Yusuke; Sato, Hikaru; Tadokoro, Shinsuke et al.
In: Organic Process Research and Development, Vol. 23, No. 4, 19.04.2019, p. 571-577.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Safe and Scalable Aerobic Oxidation by 2-Azaadamantan-2-ol (AZADOL)/NO x Catalysis

T2 - Large-Scale Preparation of Shi's Catalyst

AU - Sasano, Yusuke

AU - Sato, Hikaru

AU - Tadokoro, Shinsuke

AU - Kozawa, Masami

AU - Iwabuchi, Yoshiharu

PY - 2019/4/19

Y1 - 2019/4/19

N2 - A method for safe and scalable aerobic alcohol oxidation using 2-azaadamantan-2-ol (AZADOL), an azaadamantane-type hydroxylamine catalyst, with a NO x cocatalyst in a conventional batch reactor has been developed. The use of 2 mol % AZADOL and 10 mol % NaNO 2 was determined to promote aerobic alcohol oxidation quantitatively within a reasonable time (8 h). Safety is ensured by controlling the reaction temperature below the flash point of the acetic acid solvent. The robustness of the developed method is demonstrated by the 500 g scale oxidation of diacetone fructose into Shi's catalyst for asymmetric epoxidation.

AB - A method for safe and scalable aerobic alcohol oxidation using 2-azaadamantan-2-ol (AZADOL), an azaadamantane-type hydroxylamine catalyst, with a NO x cocatalyst in a conventional batch reactor has been developed. The use of 2 mol % AZADOL and 10 mol % NaNO 2 was determined to promote aerobic alcohol oxidation quantitatively within a reasonable time (8 h). Safety is ensured by controlling the reaction temperature below the flash point of the acetic acid solvent. The robustness of the developed method is demonstrated by the 500 g scale oxidation of diacetone fructose into Shi's catalyst for asymmetric epoxidation.

KW - aerobic oxidation

KW - alcohol oxidation

KW - hydroxylamine

KW - nitroxyl radical

KW - NO

KW - oxoammonium

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Safe and Scalable Aerobic Oxidation by 2-Azaadamantan-2-ol (AZADOL)/NO _x Catalysis: Large-Scale Preparation of Shi's Catalyst

Abstract

Keywords

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