Catalytic Oxidative Cleavage
of 1,3-Diketones to Carboxylic Acids by Aerobic Photooxidation with
Iodine

Norihiro Tada; Motoki Shomura; Lei Cui; Tomoya Nobuta; Tsuyoshi Miura; Akichika Itoh

doi:10.1055/s-0031-1289891

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Synlett 2011(19): 2896-2900
DOI: 10.1055/s-0031-1289891

LETTER

Catalytic Oxidative Cleavage of 1,3-Diketones to Carboxylic Acids by Aerobic Photooxidation with Iodine

Norihiro Tada, Motoki Shomura, Lei Cui, Tomoya Nobuta, Tsuyoshi Miura, Akichika Itoh*
Gifu Pharmaceutical University, 1-25-4, Daigaku-nishi, Gifu 501-1196, Japan
Fax: +81(58)2308105; e-Mail: itoha@gifu-pu.ac.jp;

Further Information

Publication History

Received 29 August 2011
Publication Date:
11 November 2011 (online)

Abstract
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Abstract

We report the catalytic oxidative cleavage of 1,3-diketones to the corresponding carboxylic acids by aerobic photooxidation with iodine under irradiation with a high-pressure mercury lamp.

Key words

photooxidation - aerobic - iodine - 1,3-diketone - carboxylic acid

References and Notes

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4

Typical Procedure
A solution of benzoylacetone (1, 0.3 mmol) and I₂ (0.03 mmol) in dry EtOAc (5 mL) in a Pyrex test tube, purged with an O₂ balloon, was stirred and irradiated externally with 400 W high-pressure mercury lamp for 10 h. The reaction mixture was concentrated under reduced pressure. The pure product 2 was obtained by preparative TLC.

5

These compounds were identified by comparison with authentic samples, and yields were determined by ^¹H NMR with internal standard.

6

Benzil(27) was obtained as major product in the presence of 0.5 equiv of Ca(OH)₂ under visible-light irradiation. See ref. 3f.

8

Since the reaction did not proceed when using methylene blue, a singlet-state molecular oxygen generator, instead of iodine, singlet-state molecular oxygen is probably not an active species for this reaction.