BF3 함유 이분자형 키랄 살렌 촉매에 의한 고광학순도의 에피클로로히드린 합성

이광연; 카테카라울; 김건중; Kwang-Yeon Lee; Rahul, B. Kawthekar; Geon-Joong Kim

Journal of the Korean Industrial and Engineering Chemistry, Vol.18, No.4, 330-336, August, 2007

Export Citation

BF3 함유 이분자형 키랄 살렌 촉매에 의한 고광학순도의 에피클로로히드린 합성

Synthesis of Optically pure Epichlorohydrine using Dimeric Chiral Salen Catalyst Containing BF3

이광연, 카테카라울, 김건중 ^†

인하대학교 생명화학공학부

Kwang-Yeon Lee, Rahul, B. Kawthekar, and Geon-Joong Kim^†

Th School of Chemical Engineering and Biotechnology, Inha University, Incheon 402-751, Korea

E-mail:

초록

본 연구에서는 BF3를 함유한 키랄성 코발트 살렌 촉매를 합성하고 비대칭촉매특성을 평가하였다. 촉매의 구조를 결정하기 위하여 NMR, UV 및 ESCA분석을 수행하였다. 합성한 촉매는 여러 종류의 에폭사이드 유도체의 가수분해 속도차에 의한 비대칭 고리열림반응에 적용하여 그 활성과 선택성을 조사하였다. 살렌과 BF3의 비를 다르게 하여 합성한 촉매는 전혀 다른 촉매 활성을 나타내었으며, 그 비를 2 : 1로 하여 합성한 2분자구조의 살렌착체 촉매는 물을 친핵체로 하는 라세믹 에폭사이드의 고리 열림을 통하여 99 %ee 이상의 매우 높은 광학선택성을 보였다. 특히 2분자형의 살렌 촉매는 단분자형의 촉매에 비하여 촉매량을 적게 첨가하여도 현저히 향상된 촉매활성을 나타내었고 얻어진 생성물의 분리과정에서 라세믹화를 유발시키지 않았다. 본 연구에서 적용한 촉매시스템은 키랄 에폭사이드 및 1,2-디올 중간체의 제조에 매우 효과적이었다.

In this study, new dinuclear chiral Co (salen) complexes bearing BF3 have been synthesized and their properties as the asymmetric catalyst have been examined. The NMR, UV and ESCA analyses were performed to determine the structure of synthesized catalysts. Their catalytic activity and selectivity have been demonstrated for the asymmetric ring opening of various terminal epoxides by hydrolytic kinetic resolution technology. The easily prepared dimeric complexes exhibited very high enantioselectivity for the asymmetric ring opening of epoxides with H2O nucleophile, providing enantiomerically enriched terminal epoxides (> 99 %ee). The dimeric structured chiral salen showed remakablely enhanced reactivity and may be employed substantially lower loadings than its monomeric analogues, and in addition no racemization happened during the separation of product epoxides. 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;enantioselectivity;optical isomer;hydrolytic kinetic resolution

[References]

Sheldon RA, Chirotechnology-Industrial Synthesis of Optical Active Compounds, Marcel Dekker, New York (1994)
Kagan HB, Comprehensive Asymmetric Catalysis, eds. E. N. Jacobsen, A. Pfaltz, and H. Yamamoto, Chap.2, Springer, Heidelberg (1999)
Tokunaga M, Larrow JF, Kakiuchi F, Jacobsen EN, Science, 277(5328), 936 (1997)
Schaus SE, Brandes BD, Larrow JF, Tokunaga M, Hansen KB, Gould AE, Furrow ME, Jacobsen EN, J. Am. Chem. Soc., 124(7), 1307 (2002)
Keith JM, Larrow JF, Jacobsen EN, Adv. Synth. Catal., 343, 5 (2001)
Furrow ME, Schaus SE, Jacobsen EN, J. Org. Chem., 63, 6776 (1998)
Larrow JF, Jacobsen EN, Topics in Organomet. Chem., 6, 123 (2004)
Larrow JF, Hemberger KE, Jasmine S, Kabir H, Morel P, Tetrahedron: Asymmetry, 14, 3589 (2003)
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)
Kim GJ, Lee H, Kim SJ, Tetrahedron Lett., 44, 5005 (2003)
Gluber SJ, Harris CM, Sinn E, J. Chem. Phys., 49, 2183 (1969)
Gluber SJ, Harris CM, Sinn E, Inorg. Chem., 7(2), 269 (1968)
Shibasaki M, Sasai H, Arai T, Angew. Chem.-Int. Edit., 36, 1236 (1997)
Shin CK, Kim SJ, Kim GJ, Tetrahedron Lett., 45, 7429 (2004)

[Referenced By]

[Related Articles]

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

[2] Kagan HB, Comprehensive Asymmetric Catalysis, eds. E. N. Jacobsen, A. Pfaltz, and H. Yamamoto, Chap.2, Springer, Heidelberg (1999)

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

[4] Schaus SE, Brandes BD, Larrow JF, Tokunaga M, Hansen KB, Gould AE, Furrow ME, Jacobsen EN, J. Am. Chem. Soc., 124(7), 1307 (2002)

[5] Keith JM, Larrow JF, Jacobsen EN, Adv. Synth. Catal., 343, 5 (2001)

[6] Furrow ME, Schaus SE, Jacobsen EN, J. Org. Chem., 63, 6776 (1998)

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

[8] Larrow JF, Hemberger KE, Jasmine S, Kabir H, Morel P, Tetrahedron: Asymmetry, 14, 3589 (2003)

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

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

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

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

[13] Kim GJ, Lee H, Kim SJ, Tetrahedron Lett., 44, 5005 (2003)

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

[15] Gluber SJ, Harris CM, Sinn E, Inorg. Chem., 7(2), 269 (1968)

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

[17] Shin CK, Kim SJ, Kim GJ, Tetrahedron Lett., 45, 7429 (2004)