Enzyme-catalyzed resolution of 3,8-dioxatricyclo[3.2.1.02,4]octane-6-carboxylic esters and the application to the synthesis of 3-epishikimic acid

Manabu Hamada, Yoshikazu Inami, Yasuhito Nagai, Toshinori Higashi, Mitsuru Shoji, Seiichiro Ogawa, Kazuo Umezawa, Takeshi Sugai

研究成果: Article

7 引用 (Scopus)

抄録

3,8-Dioxatricyclo[3.2.1.02,4]octane-6-carboxylic acid, whose racemic form is readily available on a large scale, is a versatile starting material for the synthesis of carbasugars and carbocyclic biologically active natural products. In this study, the enzyme-catalyzed kinetic resolution was attempted on a variety of corresponding carboxylic esters. The hydrophobic and hydrophilic properties of ester substituents greatly affected the rate of reaction and the enantioselectivity. Hydrolysis of the corresponding 2′-chloroethyl ester with pig liver esterase worked well in a highly enantioselective manner (E = 116) to give the hydrolyzate (90.6% ee) and unreacted ester recovery (99.4% ee). The hydrolyzate is a precursor for (-)-oseltamivir phosphate, and a route to (3S,4S,5R)-(-)-3-epishikimic acid was developed from the recovered ester.

元の言語English
ページ(範囲)2105-2111
ページ数7
ジャーナルTetrahedron Asymmetry
20
発行部数18
DOI
出版物ステータスPublished - 2009 9 23

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octanes
enzymes
esters
Esters
Enzymes
acids
Acids
synthesis
Carbasugars
Oseltamivir
Enzyme kinetics
swine
Enantioselectivity
Esterases
Carboxylic Acids
Biological Products
Carboxylic acids
liver
carboxylic acids
Liver

ASJC Scopus subject areas

  • Organic Chemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Catalysis

これを引用

Enzyme-catalyzed resolution of 3,8-dioxatricyclo[3.2.1.02,4]octane-6-carboxylic esters and the application to the synthesis of 3-epishikimic acid. / Hamada, Manabu; Inami, Yoshikazu; Nagai, Yasuhito; Higashi, Toshinori; Shoji, Mitsuru; Ogawa, Seiichiro; Umezawa, Kazuo; Sugai, Takeshi.

:: Tetrahedron Asymmetry, 巻 20, 番号 18, 23.09.2009, p. 2105-2111.

研究成果: Article

Hamada, Manabu ; Inami, Yoshikazu ; Nagai, Yasuhito ; Higashi, Toshinori ; Shoji, Mitsuru ; Ogawa, Seiichiro ; Umezawa, Kazuo ; Sugai, Takeshi. / Enzyme-catalyzed resolution of 3,8-dioxatricyclo[3.2.1.02,4]octane-6-carboxylic esters and the application to the synthesis of 3-epishikimic acid. :: Tetrahedron Asymmetry. 2009 ; 巻 20, 番号 18. pp. 2105-2111.
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abstract = "3,8-Dioxatricyclo[3.2.1.02,4]octane-6-carboxylic acid, whose racemic form is readily available on a large scale, is a versatile starting material for the synthesis of carbasugars and carbocyclic biologically active natural products. In this study, the enzyme-catalyzed kinetic resolution was attempted on a variety of corresponding carboxylic esters. The hydrophobic and hydrophilic properties of ester substituents greatly affected the rate of reaction and the enantioselectivity. Hydrolysis of the corresponding 2′-chloroethyl ester with pig liver esterase worked well in a highly enantioselective manner (E = 116) to give the hydrolyzate (90.6{\%} ee) and unreacted ester recovery (99.4{\%} ee). The hydrolyzate is a precursor for (-)-oseltamivir phosphate, and a route to (3S,4S,5R)-(-)-3-epishikimic acid was developed from the recovered ester.",
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AU - Higashi, Toshinori

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