Catalytic Aerobic Chemoselective α-Oxidation of Acylpyrazoles en Route to α-Hydroxy Acid Derivatives

Seiya Taninokuchi; Ryo Yazaki; Takashi Ohshima

doi:10.1021/acs.orglett.7b01293

Catalytic Aerobic Chemoselective α-Oxidation of Acylpyrazoles en Route to α-Hydroxy Acid Derivatives

Seiya Taninokuchi, Ryo Yazaki, Takashi Ohshima

Chemo-Pharmaceutical Sciences

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

24 Citations (Scopus)

Abstract

Catalytic aerobic chemoselective α-oxidation of acylpyrazoles is described. Acylpyrazoles, carboxylic acid oxidation state substrates, were efficiently oxidized under aerobic conditions using TEMPO as an oxygenating agent. The mild catalytic conditions of the present catalysis were amenable to late-stage α-oxidation of various pharmaceutical agents and natural products, leading to previously unreported α-hydroxy acid derivatives in short steps. Preliminary mechanistic studies revealed that in situ generated copper(II) peroxo species served as a Lewis acid/Brønsted base cooperative catalyst.

Original language	English
Pages (from-to)	3187-3190
Number of pages	4
Journal	Organic letters
Volume	19
Issue number	12
DOIs	https://doi.org/10.1021/acs.orglett.7b01293
Publication status	Published - Jun 16 2017

All Science Journal Classification (ASJC) codes

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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10.1021/acs.orglett.7b01293

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title = "Catalytic Aerobic Chemoselective α-Oxidation of Acylpyrazoles en Route to α-Hydroxy Acid Derivatives",

abstract = "Catalytic aerobic chemoselective α-oxidation of acylpyrazoles is described. Acylpyrazoles, carboxylic acid oxidation state substrates, were efficiently oxidized under aerobic conditions using TEMPO as an oxygenating agent. The mild catalytic conditions of the present catalysis were amenable to late-stage α-oxidation of various pharmaceutical agents and natural products, leading to previously unreported α-hydroxy acid derivatives in short steps. Preliminary mechanistic studies revealed that in situ generated copper(II) peroxo species served as a Lewis acid/Br{\o}nsted base cooperative catalyst.",

author = "Seiya Taninokuchi and Ryo Yazaki and Takashi Ohshima",

note = "Funding Information: This work was financially supported by JSPS KAKENHI Grant No. JP15H05846 in Middle Molecular Strategy, JP16H01032 in Precisely Designed Catalysts with Customized Scaffolding, Grant-in-Aid for Scientific Research (C) (No. 16K08166) and Platform for Drug Discovery, Informatics and Structural Life Science from MEXT. R.Y. thanks Ube Industries Ltd. Award in Synthetic Organic Chemistry, Japan. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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doi = "10.1021/acs.orglett.7b01293",

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AU - Taninokuchi, Seiya

AU - Yazaki, Ryo

AU - Ohshima, Takashi

N1 - Funding Information: This work was financially supported by JSPS KAKENHI Grant No. JP15H05846 in Middle Molecular Strategy, JP16H01032 in Precisely Designed Catalysts with Customized Scaffolding, Grant-in-Aid for Scientific Research (C) (No. 16K08166) and Platform for Drug Discovery, Informatics and Structural Life Science from MEXT. R.Y. thanks Ube Industries Ltd. Award in Synthetic Organic Chemistry, Japan. Publisher Copyright: © 2017 American Chemical Society.

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Y1 - 2017/6/16

N2 - Catalytic aerobic chemoselective α-oxidation of acylpyrazoles is described. Acylpyrazoles, carboxylic acid oxidation state substrates, were efficiently oxidized under aerobic conditions using TEMPO as an oxygenating agent. The mild catalytic conditions of the present catalysis were amenable to late-stage α-oxidation of various pharmaceutical agents and natural products, leading to previously unreported α-hydroxy acid derivatives in short steps. Preliminary mechanistic studies revealed that in situ generated copper(II) peroxo species served as a Lewis acid/Brønsted base cooperative catalyst.

AB - Catalytic aerobic chemoselective α-oxidation of acylpyrazoles is described. Acylpyrazoles, carboxylic acid oxidation state substrates, were efficiently oxidized under aerobic conditions using TEMPO as an oxygenating agent. The mild catalytic conditions of the present catalysis were amenable to late-stage α-oxidation of various pharmaceutical agents and natural products, leading to previously unreported α-hydroxy acid derivatives in short steps. Preliminary mechanistic studies revealed that in situ generated copper(II) peroxo species served as a Lewis acid/Brønsted base cooperative catalyst.

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Catalytic Aerobic Chemoselective α-Oxidation of Acylpyrazoles en Route to α-Hydroxy Acid Derivatives

Abstract

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