전이금속염 함유 키랄 살렌 촉매에 의한 광학선택적 에폭사이드의 합성

곽소봉; 카테카 라울; 김건중; Xiao-Feng Guo; Rahul, B. Kawthekar; Geon-Joong Kim

Korean Chemical Engineering Research, Vol.46, No.4, 769-776, August, 2008

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전이금속염 함유 키랄 살렌 촉매에 의한 광학선택적 에폭사이드의 합성

Enantioselective Epoxide Synthesis on the Chiral Salen Catalyst having a Transitional Metal Salt

곽소봉, 카테카 라울, 김건중 ^†

인하대학교 생명화학공학부, 402-751 인천시 남구 용현동 253

Xiao-Feng Guo, Rahul, B. Kawthekar, and Geon-Joong Kim^†

Department of Chemical Engineering, Inha University, 253 Yonghyun-dong, Nam-gu, Incheon 402-751, Korea

E-mail:

초록

키랄성 말단기의 에폭사이드는 키랄중간체나 여러 출발물질로서 다양하게 이용되기 때문에 그 선택적인 합성법은 매우 유용하다. 본 연구에서는 염화코발트(II), 염화철(III) 및 질산아연(II)을 각각 함유한 키랄 코발트 살렌 촉매를 새로이 합성하고 그 특성을 평가하였다. 질량분석과 EXAF분석을 통하여 형성된 촉매 착체의 구조를 평가하였다. 합성한 촉매는 방향족 에폭사이드인 스타이렌 옥사이드와 페닐글리시딜 에테르의 속도차에 의한 비대칭 가수분해적 고리 열림반응과 글리시틸부틸레이트의 합성반응에 적용하여 그 활성과 선택성을 조사하였다. 합성이 용이한 전이금속염함유 살렌착체 촉매는 물을 친핵체로 하는 라세믹 에폭사이드의 고리 열림을 통하여 99%ee 이상을 나타낼 정도의 매우 높은 광학선택성을 보였으며, 적은 양의 첨가로도 높은 활성을 보였다. 본 연구에서 적용한 촉매씨스템은 키랄 에폭사이드 및 1,2-디올 중간체의 제조에 매우 효과적이었다.

The stereoselective synthesis of chiral terminal epoxide is of immense interest due to their utility as versatile starting materials as well as chiral intermediates. In this study, new chiral Co(salen) complexes bearing cobalt(II) chloride, iron(III) chloride and zinc(II) nitrate have been synthesized and characterized. The mass and EXAFS spectra provided the direct evidence of formation of complex. Their catalytic activity and selectivity have been demonstrated for the asymmetric ring opening of terminal epoxides such as styrene oxide and phenylglycidylether by hydrolytic kinetic resolution technology and for the synthesis of glycidyl buthylate. The easily prepared complexes exhibited very high enantioselectivity for the asymmetric ring opening of epoxides with H2O nucleophile, providing enantiomerically enriched terminal epoxides (>99% ee). The newly synthesized chiral salen showed remakablely enhanced reactivity with substantially low loadings. The system described in this work is very efficient for the sinthesis of chiral epoxide and 1,2-diol intermediates

Keywords:Chiral Salen;Asymmetric Ring Opening;Epoxide;Enantioselectivity;Optical Isomer;Hydrolytic Kinetic Resolution

[References]

Sheldon RA, Chirotechnology-Industrial Synthesis of Optical Active Compounds, Marcel Kekker, New York (1994)
Ready JM, Jacobsen EN, J. Am. Chem. Soc., 121(25), 6086 (1999)
Kagan HB, in Jacobsen, E. N., Pfaltz, A. and Yamamoto, H. (Ed.), Comprehensive Asymmetric Catalysis : Historical Perspective, Springer, Heidelberg, Chap.2 (1999)
Schaus SE, Branalt J, Jacobson EN, J. Org. Chem., 63, 403 (1998)
Lebel H, Jacobson EN, Tetrahedron Lett., 40, 7303 (1999)
Tokunaga M, Larrow JF, Kakiuchi F, Jacobsen EN, Science, 277(5328), 936 (1997)
Savle PS, Lamoreaux MJ, Berry JF, Gandour RD, Tetrahedron: Asymmetry, 9, 1843 (1998)
Larrow JF, Jacobsen EN, Topics in Organomet. Chem., 6, 123 (2004)
Gluber SJ, Harris CM, Sinn E, J. Chem. Phys., 49, 2183 (1969)
Gluber SJ, Harris CM, Sinn E, Inorg. Chem., 7(2), 268 (1968)
Thakur SS, Li W, Kim SJ, Kim GJ, Tetrahedron Lett., 46, 2263 (2005)
Kawthekar RB, Kim GJ, Helvetica Chimica Acta, 91, 317 (2008)
Annis DA, Jacobsen EN, J. Am. Chem. Soc., 121(17), 4147 (1999)
Konsler RG, Karl J, Jacobsen EN, J. Am. Chem. Soc., 120(41), 10780 (1998)
Ready JM, Jacobsen EN, J. Am. Chem. Soc., 123(11), 2687 (2001)
Ready JM, Jacobsen EN, Angew. Chem. Int. Ed., 41, 1374 (2002)
Shibasaki M, Sasai H, Arai T, Angew. Chem.-Int. Edit., 36, 1236 (1997)

[Related Articles]

[1] Sheldon RA, Chirotechnology-Industrial Synthesis of Optical Active Compounds, Marcel Kekker, New York (1994)

[2] Ready JM, Jacobsen EN, J. Am. Chem. Soc., 121(25), 6086 (1999)

[3] Kagan HB, in Jacobsen, E. N., Pfaltz, A. and Yamamoto, H. (Ed.), Comprehensive Asymmetric Catalysis : Historical Perspective, Springer, Heidelberg, Chap.2 (1999)

[4] Schaus SE, Branalt J, Jacobson EN, J. Org. Chem., 63, 403 (1998)

[5] Lebel H, Jacobson EN, Tetrahedron Lett., 40, 7303 (1999)

[6] Tokunaga M, Larrow JF, Kakiuchi F, Jacobsen EN, Science, 277(5328), 936 (1997)

[7] Savle PS, Lamoreaux MJ, Berry JF, Gandour RD, Tetrahedron: Asymmetry, 9, 1843 (1998)

[8] Larrow JF, Jacobsen EN, Topics in Organomet. Chem., 6, 123 (2004)

[9] Gluber SJ, Harris CM, Sinn E, J. Chem. Phys., 49, 2183 (1969)

[10] Gluber SJ, Harris CM, Sinn E, Inorg. Chem., 7(2), 268 (1968)

[11] Thakur SS, Li W, Kim SJ, Kim GJ, Tetrahedron Lett., 46, 2263 (2005)

[12] Kawthekar RB, Kim GJ, Helvetica Chimica Acta, 91, 317 (2008)

[13] Annis DA, Jacobsen EN, J. Am. Chem. Soc., 121(17), 4147 (1999)

[14] Konsler RG, Karl J, Jacobsen EN, J. Am. Chem. Soc., 120(41), 10780 (1998)

[15] Ready JM, Jacobsen EN, J. Am. Chem. Soc., 123(11), 2687 (2001)

[16] Ready JM, Jacobsen EN, Angew. Chem. Int. Ed., 41, 1374 (2002)

[17] Shibasaki M, Sasai H, Arai T, Angew. Chem.-Int. Edit., 36, 1236 (1997)