제올라이트-효소 촉매를 이용한 ρ,α-Dimethyl Benzyl Alcohol의 2상 동적 속도론적 광학분할

차연주; 고문규; 박융호; Yeon-Ju Cha; Moon-Kyu Ko; Yeung-Ho Park

Journal of the Korean Industrial and Engineering Chemistry, Vol.17, No.6, 658-664, December, 2006

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제올라이트-효소 촉매를 이용한 ρ,α-Dimethyl Benzyl Alcohol의 2상 동적 속도론적 광학분할

Biphasic Dynamic Kinetic Resolution of ρ,α-Dimethyl Benzyl Alcohol over Zeolite-Enzyme Catalysts

차연주, 고문규¹, 박융호 ^†

한양대학교 재료화학공학부
¹건양대학교 화학생명공학과

Yeon-Ju Cha, Moon-Kyu Ko¹, and Yeung-Ho Park^†

Division of Materials and Chemical Engineering, Hanyang University, Ansan 425-791, Korea
¹Department of Chemical and Biochemical Engineering, Konyang University, Nonsan 320-711, Korea

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초록

ρ,α-dimethyl benzyl alcohol을 효과적으로 분할하기 위하여 2상 동적 속도론적 광학분할(biphasic dynamic kinetic resolution, DKR)반응을 실시하였다. 라세미화 반응을 위하여 촉매로 산성 제올라이트를 사용하였고 속도론적 광학분할(kinetic resolution, KR)을 위하여 고정화 효소를 촉매로 사용하였다. 유기용매와 물을 용매로 사용하는 이상 DKR 반응에서, acyl donor, 반응온도, 기질의 농도, 두 가지 촉매의 상대적 비율 및 교반속도 등의 공정변수를 변화시켜가면서 DKR반응의 전환율과 생성물의 광학순도에 미치는 영향을 조사하였다. 그 결과, ρ,α-dimethyl benzyl alcohol의 DKR 반응에서 99% 이상의 광학순도를 가지는 생성물을 최대 88%의 높은 수율로 얻을 수 있었으며, 높은 TON에서도 반응의 효율성이 유지되었고 촉매의 재사용 시에도 지속적인 활성을 나타내었다.

ρ,α-dimethyl benzyl alcohol was resolved by the biphasic dynamic kinetic resolution (DKR). Acidic zeolite was used as a racemization catalyst while immobilized enzyme was employed for kinetic resolution. The effects of the process variables including nature of acyl donor, reaction temperature, substrate concentration, ratio of the two catalysts and stirring rate on the conversion and enantiomeric purity of the product were investigated. In DKR of ρ,α-dimethyl benzyl alcohol, the product of 99% ee was obtained with a maximum yield of 88%. The high performance of the catalyst system was maintained in the condition of higher TON and under repeated use.

Keywords:biphasic dynamic kinetic resolution;ρ,α-dimethyl benzyl alcohol;acidic zeolite;immobilized enzyme;process variables

[References]

Kim MJ, Ahn Y, Park J, Curr. Opin. Biotechnol., 13, 578 (2002)
El Gihani MT, Williams JMJ, Curr. Opin. Biotechnol., 3, 11 (1999)
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Reetz MT, Schimossek K, Chimia, 50, 668 (1996)
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House DW, US Patent 5,476,964 (1995)
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Wuyts S, De Temmerman K, De Vos DE, Jacobs PA, Chem. Eur. J., 11, 386 (2005)

[Related Articles]

[1] Kim MJ, Ahn Y, Park J, Curr. Opin. Biotechnol., 13, 578 (2002)

[2] El Gihani MT, Williams JMJ, Curr. Opin. Biotechnol., 3, 11 (1999)

[3] Panke S, Wubbolts MG, Curr. Opin. Biotechnol., 13, 11 (2002)

[4] Allen JV, Williams JMJ, Tetrahedron Lett., 37, 1859 (1996)

[5] Dinh PM, Howarth JA, Hudnott AR, Williams JMJ, Harris W, Tetrahedron Lett., 37, 7623 (1996)

[6] Persson BA, Larsson ALE, Ray ML, Backvall JE, J. Am. Chem. Soc., 121, 1645 (1999)

[7] Rauhi MA, Chem. Eng. News, 80, 45 (2002)

[8] Reetz MT, Schimossek K, Chimia, 50, 668 (1996)

[9] Wuyts S, De Vos DE, Verpoort F, Depla D, De Gryse R, Jacobs PA, J. Catal., 219(2), 417 (2003)

[10] House DW, US Patent 5,476,964 (1995)

[11] Kalliney SY, Ruggeri MV, WO Patent 91/08196 (1991)

[12] Wuyts S, Temmerman K, De vos D, Jacobs P, Chem. Commun., 1928 (2003)

[13] Wuyts S, De Temmerman K, De Vos DE, Jacobs PA, Chem. Eur. J., 11, 386 (2005)