Facile and Efficient Oxidative Transformation of Primary Alcohols to Methyl Esters in Water Using Hypervalent Iodine(III) Reagents

Hirofumi Tohma; Tomohiro Maegawa; Yasuyuki Kita

doi:10.1055/s-2003-38373

LETTER

Facile and Efficient Oxidative Transformation of Primary Alcohols to Methyl Esters in Water Using Hypervalent Iodine(III) Reagents

Hirofumi Tohma, Tomohiro Maegawa, Yasuyuki Kita*
Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamada-oka, Suita, Osaka, 565-0871, Japan
Fax: +81(6)68798229; e-Mail: kita@phs.osaka-u.ac.jp;

Abstract

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Abstract

A facile and direct oxidative esterification of primary alcohols in water using a combination of the hypervalent iodine(III) reagent, iodosobenzene (PhIO), and KBr has been developed. This methodology is expected to be environmentally benign since it uses a recyclable polymer-supported iodine(III) reagent in water.

Key words

alcohols - oxidations - esterification - hypervalent iodine - polymers

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References

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General Experimental Procedure: Oxidation with PhIO-KBr: To a stirred solution of 1 (1.0 mmol) and KBr (0.5 mmol) in MeOH (1 mL) was added dropwise 0.5 N HCl aq (0.5 mL). PhIO (3.5 mmol) was added to the vigorously stirred solution and stirring was continued for several hours at room temperature while checking the reaction progress by GC or TLC. After completion of the reaction, water (ca. 1.5 mL) was added to the mixture. The mixture was filtrated through BOND ELUT C 18 (Varian), washed with a small amount of water, and extracted with Et₂O. The filtrate was dried with MgSO₄, and evaporated. The residue was purified by column chromatography (SiO₂/n-hexane-Et₂O) to give pure 2. Oxidation with PDAIS-KBr: To a stirred solution of 1 (1.0 mmol) and KBr (1.0 mmol) in MeOH (2 mL) was added dropwise 0.5 N HCl aq (1 mL). PDAIS (prepared by the reported procedure [9b] ) (3.0 mmol) was added to the vigorously stirred solution and stirring was continued for several hours at room temperature. After completion of the reaction, water (ca. 3 mL) was added to the mixture. The mixture was filtered through BOND ELUT C 18 (Varian) and washed with a small amount of water to remove KBr. The residue was extracted with Et₂O, and the filtrate was dried and evaporated. The residue was purified by column chromatography to give pure 2.