새로운 구조의 키랄 살렌 촉매상에서 페놀유도체에 의한 에폭사이드의 광학선택적 개환반응

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

Journal of the Korean Industrial and Engineering Chemistry, Vol.18, No.6, 630-635, December, 2007

Export Citation

새로운 구조의 키랄 살렌 촉매상에서 페놀유도체에 의한 에폭사이드의 광학선택적 개환반응

Enantioselective Phenolic Kinetic Resolution of Epoxides Catalyzed by New Chiral Salen Complexes

카테카라울, 이광연, 김건중 ^†

인하대학교 생명화학공학부

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

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

E-mail:

초록

구조중에 1개의 tert-부틸기를 가진 새로운 형태의 키랄살렌 착체를 합성하여 비대칭반응 촉매로서 활용하였다. 알루미늄족의 금속염을 소유한 이량체형의 키랄 살렌 촉매는 에폭사이드의 산소고리를 페놀류로 여는 비대칭반응에서 매우 높은 활성과 선택성을 나타내었다. 또한 무기담체에 고정화된 살렌 착체도 이 반응에 대하여 효과적인 촉매로 사용할 수 있었다. 새로운 키랄 살렌촉매 중에 존재하는 금속염의 종류는 광학선택적 반응에서 중요한 영향을 나타내었다.

New chiral Co-salen complexes with one C3-tBu group in the structure have been synthesized and applied as a chiral catalyst. A dimeric chiral salen having aluminum group metal salts such as AlCl3 displayed very high catalytic reactivity and enantioselectivity for the asymmetric ring opening of epoxides to synthesize optically pure α-aryloxy alcohols via phenolic kinetic resolution. The salen complexes immobilized on the inorganic support were also used as effective catalysts in that reaction. The identity of metal salts in the new chiral salen complex has proved to be important in the enantioselective reactions.

Keywords:heterometallic salen;phenolic kinetic resolution;α-aryloxy alcohols;terminal epoxides

[References]

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Ready JM, Jacobsen EN, J. Am. Chem. Soc., 123(11), 2687 (2001)
Shibasaki M, Yoshikawa N, Chem. Rev., 102(6), 2187 (2002)
Smitha MA, Prasad E, Gopidas KR, J. Am. Chem. Soc., 123(6), 1159 (2001)
Mermerian AH, Fu GC, J. Am. Chem. Soc., 125(14), 4050 (2003)
Yang M, Zhu C, Yuan F, Huang Y, Pan Y, Org. Lett., 7, 1927 (2005)
Kwon MA, Kim GJ, Catal. Today, 87(1-4), 145 (2003)
Kim GJ, Shin J, Tetrahedron Lett., 40, 6827 (1999)
Bose SD, Bioorg. Med. Chem., 13, 627 (2005)
White DE, Jacobson EN, Tetrahedron: Asymmetry, 14, 3633 (2003)
Konsler RG, Karl J, Jacobsen EN, J. Am. Chem. Soc., 120(41), 10780 (1998)
Peukert S, Jacobsen EN, Org. Lett., 1, 1245 (1999)
Ready JM, Jacobsen EN, Angew Chem. Int. Ed., 41, 1374 (2002)
Breinbauer R, Jacobsen EN, Angew. Chem.-Int. Edit., 39, 3604 (2000)
Thakur SS, Li W, Kim SJ, Kim GJ, Tetrahedron Lett., 46, 2263 (2005)
Thakur SS, Li W, Shin CK, Kim GJ, Chirality, 18, 37 (2006)
Bartoli G, Bosco M, Carlone A, Locatelli M, Massaccesi M, Melchiorre P, Sambri L, Org. Lett., 6, 2173 (2004)
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Atwood D, Wei P, Chem. Commun., 1427 (1997)
Solari E, Corazza F, Floriani C, Chiesi-Villa A, Guastini C, J. Chem. Soc.-Dalton Trans., 1345 (1990)
Gruber SJ, Harris CM, Sinn E, Inorg. Chem., 2, 268 (1968)
Holm RH, Everett W, Chakravorty A, Prog. Inorg. Chem., 7, 83 (1966)
Aoi H, Ishimori M, Tsuruta T, Bull. Chem. Soc. Jpn., 48, 1897 (1975)

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

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

[3] Shibasaki M, Yoshikawa N, Chem. Rev., 102(6), 2187 (2002)

[4] Smitha MA, Prasad E, Gopidas KR, J. Am. Chem. Soc., 123(6), 1159 (2001)

[5] Mermerian AH, Fu GC, J. Am. Chem. Soc., 125(14), 4050 (2003)

[6] Yang M, Zhu C, Yuan F, Huang Y, Pan Y, Org. Lett., 7, 1927 (2005)

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

[8] Kim GJ, Shin J, Tetrahedron Lett., 40, 6827 (1999)

[9] Bose SD, Bioorg. Med. Chem., 13, 627 (2005)

[10] White DE, Jacobson EN, Tetrahedron: Asymmetry, 14, 3633 (2003)

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

[12] Peukert S, Jacobsen EN, Org. Lett., 1, 1245 (1999)

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

[14] Breinbauer R, Jacobsen EN, Angew. Chem.-Int. Edit., 39, 3604 (2000)

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

[16] Thakur SS, Li W, Shin CK, Kim GJ, Chirality, 18, 37 (2006)

[17] Bartoli G, Bosco M, Carlone A, Locatelli M, Massaccesi M, Melchiorre P, Sambri L, Org. Lett., 6, 2173 (2004)

[18] Bartoli G, Bosco M, Carlone A, Locatelli M, Melchiorre P, Sambri L, Org. Lett., 6, 3973 (2004)

[19] Atwood DA, Harvey MJ, Chem. Rev., 101(1), 37 (2001)

[20] Atwood D, Wei P, Chem. Commun., 1427 (1997)

[21] Solari E, Corazza F, Floriani C, Chiesi-Villa A, Guastini C, J. Chem. Soc.-Dalton Trans., 1345 (1990)

[22] Gruber SJ, Harris CM, Sinn E, Inorg. Chem., 2, 268 (1968)

[23] Holm RH, Everett W, Chakravorty A, Prog. Inorg. Chem., 7, 83 (1966)

[24] Aoi H, Ishimori M, Tsuruta T, Bull. Chem. Soc. Jpn., 48, 1897 (1975)