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Synlett 2010(13): 1979-1983  
DOI: 10.1055/s-0030-1258134
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Direct Synthesis of 1,2-Diketones by Catalytic Aerobic Oxidative Decarboxylation of 1,3-Diketones with Iodine and Base under Irradiation of Fluorescent Light

Norihiro Tada, Motoki Shomura, Hiroki Nakayama, Tsuyoshi Miura, Akichika Itoh*
Gifu Pharmaceutical University, 1-25-4, Daigaku-nishi, Gifu 501-1196, Japan
Fax: +81(58)2308108; e-Mail: itoha@gifu-pu.ac.jp;
Further Information

Publication History

Received 27 April 2010
Publication Date:
09 July 2010 (online)

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Abstract

We report a catalytic direct synthesis of 1,2-diketone from 1,3-diketone through iodine/base-catalyzed aerobic photo­oxidation under visible-light irradiation of fluorescent lamp.

Key words

photooxidation - iodine - aerobic - 1,3-diketone - ­1,2-diketone

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21

Typical Procedure
A solution of dibenzoylmethane (1a, 0.3 mmol), I2 (0.003 mmol), and Ca(OH)2 (0.15 mmol) in dry EtOAc (5 mL) in a Pyrex test tube, purged with an O2 balloon, was stirred and irradiated externally with four of 22 W fluorescent lamps for 10 h. The reaction mixture was concentrated under reduced pressure. The pure product 2a was obtained by preparative TLC.

22

Iodide 5, which is provided by alternative method, is converted into 2a in 66% yield under our standard conditions in the absence of I2.