Unique Salt Effect on Highly Selective Synthesis of Acid-Labile Terpene and Styrene Oxides with a Tungsten/H2O2 Catalytic System under Acidic Aqueous Conditions

Houjin Hachiya; Yoshihiro Kon; Yutaka Ono; Kiyoshi Takumi; Naoki Sasagawa; Yoichiro Ezaki; Kazuhiko Sato

doi:10.1055/s-0031-1290948

Synthesis, Table of Contents

Synthesis 2012; 44(11): 1672-1678
DOI: 10.1055/s-0031-1290948

paper

Unique Salt Effect on Highly Selective Synthesis of Acid-Labile Terpene and Styrene Oxides with a Tungsten/H₂O₂ Catalytic System under Acidic Aqueous Conditions

Houjin Hachiya

^aNational Institute of Advanced Industrial Science and Technology (AIST), Central 5 Higashi 1-1-1, Tsukuba, Ibaraki, 305-8565, Japan, Fax: +81(29)8614670 Email: y-kon@aist.go.jp

,

Yoshihiro Kon*

^aNational Institute of Advanced Industrial Science and Technology (AIST), Central 5 Higashi 1-1-1, Tsukuba, Ibaraki, 305-8565, Japan, Fax: +81(29)8614670 Email: y-kon@aist.go.jp

,

Yutaka Ono

^aNational Institute of Advanced Industrial Science and Technology (AIST), Central 5 Higashi 1-1-1, Tsukuba, Ibaraki, 305-8565, Japan, Fax: +81(29)8614670 Email: y-kon@aist.go.jp

,

Kiyoshi Takumi

^bArakawa Chemical Industries, Ltd., 5, Okubo, Tsukuba, Ibaraki, 300-2611, Japan

,

Naoki Sasagawa

^bArakawa Chemical Industries, Ltd., 5, Okubo, Tsukuba, Ibaraki, 300-2611, Japan

,

Yoichiro Ezaki

^bArakawa Chemical Industries, Ltd., 5, Okubo, Tsukuba, Ibaraki, 300-2611, Japan

,

Kazuhiko Sato*

^aNational Institute of Advanced Industrial Science and Technology (AIST), Central 5 Higashi 1-1-1, Tsukuba, Ibaraki, 305-8565, Japan, Fax: +81(29)8614670 Email: y-kon@aist.go.jp

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Abstract

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Abstract

Acid-labile epoxides such as terpene and styrene oxides are effectively synthesized in high yields with good selectivities using tungsten-catalyzed hydrogen peroxide epoxidation in the presence of Na₂SO₄. The salt effect is thought to originate with the addition of a saturated amount of Na₂SO₄ to aqueous H₂O₂; this addition strongly inhibited the undesired hydrolysis of the acid-labile epoxy products, despite the biphasic conditions of substrate as oil phase and H₂O₂ as acidic aqueous phase.

Key words

oxidation - catalysis - epoxides - terpenoids - green chemistry

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References

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