이량체구조를 갖는 키랄 살렌 촉매를 이용한 고 광학순도의 에폭사이드 화합물 합성

김건중; 김성진; 이문희; 진숙위; 신창교; 타쿼산토쉬; Geon-Joong Kim; Seong-Jin Kim; Wenji Li; Shu-Wei Chen; Chang-Kyo Shin; Santosh S. Thakur

Korean Chemical Engineering Research, Vol.43, No.6, 647-661, December, 2005

Export Citation

이량체구조를 갖는 키랄 살렌 촉매를 이용한 고 광학순도의 에폭사이드 화합물 합성

Synthesis of Enantiopure Epoxide Compounds Using Dimeric Chiral Salen Catalyst

김건중 ^†, 김성진¹, 이문희, 진숙위, 신창교, 타쿼산토쉬

인하대학교 생명화학공학부, 402-701 인천시 남구 용현동 253
¹(주) 알에스텍, 306-230 대전시 대덕구 신일동 1688-5

Geon-Joong Kim^†, Seong-Jin Kim¹, Wenji Li, Shu-Wei Chen, Chang-Kyo Shin, and Santosh S. Thakur

Department of Chemical Engineering, Inha University, 253, Yonghyun-dong, Nam-gu, Incheon 402-701, Korea
¹Department of Chemical Engineering, RStech Corp., #305 Venture Town, 1688-5, Sinil-dong, Daedeok-gu, Daejeon 306-230, Korea

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초록

키랄성 말단기의 에폭사이드는 키랄중간체나 여러 출발물질로서 다양하게 이용되기 때문에 입체선택적인 학술적으로나 산업적인 관점에서 대단히 흥미롭다. 본 총설에서는 키랄성 코발트 살렌을 이용한 비대칭 고리열림 반응에 대한 연구개발동향을 고찰하였다. 여러 가지 가능한 합성방법 중에서 가수분해의 속도차에 의한 분리반응기술은 높은 광학순도의 터미널 에폭사이드를 합성할 수 있는 탁월한 방법이다. 본 저자들은 균일계 및 불균일계의 키랄성 이핵성 살렌 착체를 합성하여, 에폭사이드의 고리를 여러 종류의 친핵체로 광학선택적으로 열고 다시 선택적으로 고리화시키는 한 단계의 반응에 대하여 그들의 활성을 조사하였다. 촉매와 염기 존재하에서 고리 열림과 닫음 반응을 조합시킴으로써 고수율로 높은 광학순도의 에폭사이드를 제조할 수 있었다. 이들 촉매는 공업적인 규모로 키랄 중간체를 생산하는데 이용되고 있다. 본 논문에서는 가수분해 속도차이에 따른 분리반응 기술을 적용하여 여러 종류의 키랄성 화합물을 제조한 연구실험 결과를 서술하였다.

The stereoselective synthesis of chiral terminal epoxide is of immense academic and industrial interest due to their utility as versatile starting materials as well as chiral intermediates. In this review, we investigate the research and development trend in the asymmetric ring opening reactions using cobalt salen catalysts. Hydrolytic kinetic resolution (HKR) technology is the very prominent way to prepare optically pure terminal epoxides among available methods. We have synthesized homogeneous and heterogeneous chiral dinuclear salen complexes and demonstrated their catalytic activity and selectivity for the asymmetric ring opening of terminal epoxides with variety of nucleophiles and for asymmetric cyclization to prepare optically pure terminal epoxides in one step. The resolved ring opened product combined with ring closing in the presence of base and catalyst afforded the enantioriched terminal epoxides in quantitaive yield. Potentially, these catalysts are using on an industrial scale to produce chiral intermediates. The experimental results of HKR technology applied to the synthesis of various chiral compounds are presented in this paper.

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

[References]

Noyori R, Asymmetric Catalysis in Organic Synthesis, John Wiely, New York (1994)
Sheldon RA, Chirotechnology-Industrial Synthesis of Optical Active Compounds, Marcel Dekker, New York (1994)
Noyori R, Hashiguchi S, Accounts Chem. Res., 30(2), 97 (1997)
Gao Y, Hanson RM, Klunder JM, Ko SY, Masamune H, Sharpless KB, J. Am. Chem. Soc., 109(19), 5765 (1987)
Kagan HB, Jacobsen EN, Pfaltz A, Yamamoto H, (Ed.), Comprehensive Asymmetric Catalysis, Springer, Heidelberg, chap.2 (1999)
Aoi H, Ishimori M, Yoshikawa S, Tsuruta T, J. Org. Chem., 85, 241 (1975)
Larrow JF, Jacobsen EN, J. Org. Chem., 59(7), 1939 (1994)
Larrow JF, Jacobsen EN, Topics in Organomet. Chem., 6, 123 (2004)
Zhang W, Jacobson EN, J. Org. Chem., 56(7), 2296 (1991)
Brandes BD, Jacobsen EN, J. Org. Chem., 59(16), 4378 (1994)
Brandes BD, Jacobsen EN, Tetahedron; Asymmetry, 8(23), 3927 (1997)
Palucki M, McCormick GJ, Jacobsen EN, Tetrahedron Lett., 36(31), 5457 (1995)
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(1), 5 (2001)
Furrow ME, Schaus SE, Jacobsen EN, J. Org. Chem., 63(20), 6776 (1998)
Larrow JF, Hemberger KE, Jasmin S, Kabir H, Morel P, Tetrahedron: Asymmetry, 14(22), 3589 (2003)
Kim GJ, Lee H, Kim SJ, Tetrahedron Lett., 44(27), 5005 (2003)
Thakur SS, Li W, Kim SJ, Kim GJ, Tetrahedron Lett., 46(13), 2263 (2005)
Gruber SJ, Harris CM, Sinn E, J. Chem. Phys., 49(5), 2183 (1968)
Iida T, Yamamoto N, Matsunaga S, Woo HG, Shibasaki M, Angew. Chem.-Int. Edit., 37(16), 2223 (1998)
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)
Kim GJ, Park DW, Catal. Today, 63(2-4), 537 (2000)
Kim GJ, Shin JH, Tetrahedron Lett., 40(37), 6827 (1999)
Kwon MA, Kim GJ, Catal. Today, 87(1-4), 145 (2003)
Shin CK, Kim SJ, Kim GJ, Tetrahedron Lett., 45(40), 7429 (2004)
Bodor N, ElKousai A, Kano M, Nakamura T, J. Med. Chem., 31(1), 100 (1988)

[Related Articles]

[1] Noyori R, Asymmetric Catalysis in Organic Synthesis, John Wiely, New York (1994)

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

[3] Noyori R, Hashiguchi S, Accounts Chem. Res., 30(2), 97 (1997)

[4] Gao Y, Hanson RM, Klunder JM, Ko SY, Masamune H, Sharpless KB, J. Am. Chem. Soc., 109(19), 5765 (1987)

[5] Kagan HB, Jacobsen EN, Pfaltz A, Yamamoto H, (Ed.), Comprehensive Asymmetric Catalysis, Springer, Heidelberg, chap.2 (1999)

[6] Aoi H, Ishimori M, Yoshikawa S, Tsuruta T, J. Org. Chem., 85, 241 (1975)

[7] Larrow JF, Jacobsen EN, J. Org. Chem., 59(7), 1939 (1994)

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

[9] Zhang W, Jacobson EN, J. Org. Chem., 56(7), 2296 (1991)

[10] Brandes BD, Jacobsen EN, J. Org. Chem., 59(16), 4378 (1994)

[11] Brandes BD, Jacobsen EN, Tetahedron; Asymmetry, 8(23), 3927 (1997)

[12] Palucki M, McCormick GJ, Jacobsen EN, Tetrahedron Lett., 36(31), 5457 (1995)

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

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

[15] Keith JM, Larrow JF, Jacobsen EN, Adv. Synth. Catal., 343(1), 5 (2001)

[16] Furrow ME, Schaus SE, Jacobsen EN, J. Org. Chem., 63(20), 6776 (1998)

[17] Larrow JF, Hemberger KE, Jasmin S, Kabir H, Morel P, Tetrahedron: Asymmetry, 14(22), 3589 (2003)

[18] Kim GJ, Lee H, Kim SJ, Tetrahedron Lett., 44(27), 5005 (2003)

[19] Thakur SS, Li W, Kim SJ, Kim GJ, Tetrahedron Lett., 46(13), 2263 (2005)

[20] Gruber SJ, Harris CM, Sinn E, J. Chem. Phys., 49(5), 2183 (1968)

[21] Iida T, Yamamoto N, Matsunaga S, Woo HG, Shibasaki M, Angew. Chem.-Int. Edit., 37(16), 2223 (1998)

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

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

[24] Kim GJ, Park DW, Catal. Today, 63(2-4), 537 (2000)

[25] Kim GJ, Shin JH, Tetrahedron Lett., 40(37), 6827 (1999)

[26] Kwon MA, Kim GJ, Catal. Today, 87(1-4), 145 (2003)

[27] Shin CK, Kim SJ, Kim GJ, Tetrahedron Lett., 45(40), 7429 (2004)

[28] Bodor N, ElKousai A, Kano M, Nakamura T, J. Med. Chem., 31(1), 100 (1988)