페로센을 이용한 비대칭 유기합성용 금속 촉매의 개발

오영희; 최미진

Journal of the Korean Industrial and Engineering Chemistry, Vol.10, No.5, 804-807, August, 1999

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페로센을 이용한 비대칭 유기합성용 금속 촉매의 개발

Development of Ferrocene-Containing Metal Catalysts for Asymmetric Synthesis

오영희, 최미진

초록

페로센 카르복시알데히드와 1,2-diaminocyclohexane을 2:1로 반응시켜 키랄 리간드 L(L=N,N''-cyclohexane bis(ferrocenylmethylene)amine)을 합성하고 이를 구리와 반응시켜 새로운 구리 착물을 합성하였다. 이 착물들을 확인하고 비대칭 유기 합성반응에 촉매로 사용하였다. 구리(II) 착물들은 스티렌과 에틸디아조아세테이트와의 시클로프로판화 반응에서 촉매작용을 하지 않았으나 구리(I)화합물, Cu(I)LOTf (OTf=trifluoromethanesulfonate)는 시클로프로판 생성물 trans:cis의 비율에 있어 80:20 이상의 높은 regioselectivity를 보였다.

New copper complexes with a ligand, L(L=N,N`-cyclohexane bis(ferrocenylmethylene)amine) which was obtained from ferrocene carboxaldehyde and 1,2-diaminocyclohexane with a mole ratio of 2:1, were prepared and characterized. Those were adapted to asymmetric catalysis. The copper(II) complexes do not work in cyclopropanation of styrene and ethyl diazoacetate but copper(I) complex catalyzes. The Cu(I)LOTf (OTf=trifluorometanesulfonate) shows a good regioselectivity giving high trans to cis ratio of up to 80:20.

Keywords:Asymmetric catalysis;Cyclopropanation;Copper;Regioselectivity;Enantioselectivity

[References]

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Doyle MP, Chem. Rev., 86, 919 (1986)
Davies IW, Gerena L, Cai D, Larsen RD, Verhoeven TR, Reider PJ, Tetrahedron Lett., 38, 1145 (1997)
Sundberg RJ, Pitts WJ, J. Org. Chem., 45, 3048 (1991)
Ito K, Katsuki T, Tetrahedron Lett., 34, 2661 (1993)
Sawamura M, Ito Y, Chem. Rev., 92, 857 (1992)
Evans DA, Woerpel KA, Hinmal MM, Faul MM, J. Am. Chem. Soc., 113, 726 (1991)
Bedekar AV, Andersson PG, Tetrahedron Lett., 37, 4073 (1996)
Muller D, Umbricht G, Weber B, Pfaltz A, Helv. Chim. Acta, 74, 232 (1991)
Lowenthal RE, Masamune S, Tetrahedron Lett., 32, 7373 (1991)
Fraile JM, Garcia JI, Mayoral JA, Tarnal T, Tetrahedron: Asymmetry, 8, 2089 (1997)
Leutenegger U, Umbricht G, Fahrni C, von Matt P, Pfaltz A, Tetrahedron, 48, 2143 (1992)
Harm AM, Knight JG, Stemp G, Tetrahedron Lett., 37, 6189 (1996)
Bedekar AV, Koroleva EB, Andersson PG, J. Org. Chem., 62, 2518 (1997)
Fritschi H, Leutenegger U, Siegmann K, Pfaltz A, Helv. Chim. Acta, 71, 1541 (1988)
Kanemasa S, Hamura S, Harada E, Yamamoto H, Tetrahedron Lett., 35, 7985 (1994)
Kim HS, Kim JW, Kwon SC, Shim SC, Kim TJ, J. Org. Chem., 545 (1997)
Vanveggel FC, Verboom W, Reinhoudt DN, Chem. Rev., 94(2), 279 (1994)
Togni A, Breutel C, Schnyder A, Spindler F, Landert H, Tijani A, J. Am. Chem. Soc., 116(9), 4062 (1994)
Cullen WR, Evans SV, Han NF, Trotter J, Inorg. Chem., 26, 514 (1987)
Kim SG, Cho CW, Ahn KH, Tetrahedron: Asymmetry, 8, 1023 (1997)
Benito A, Cano J, Manez RM, Soto J, Paya J, Lloret F, Julve M, Faus J, Marcos MD, Inorg. Chem., 32, 1197 (1993)
Green J, Sinn E, Woodward S, Polyhedron, 12, 991 (1993)
Nlate S, Herdtweck E, Blumel J, Fischer RA, J. Org. Chem., 97, 545 (1997)
Ichiyanagi T, Shimizu M, Fujisawa T, Tetrahedron, 53, 9599 (1997)
Doyle MP, Accounts Chem. Res., 19, 348 (1986)
Uozumi Y, Kyota H, Kishi E, Kitayama K, Hayashi T, Tetrahedron, 7, 1603 (1996)

[1] Lowenthal RE, Abiko A, Masamune S, Tetrahedron Lett., 31, 6005 (1990)

[2] Doyle MP, Chem. Rev., 86, 919 (1986)

[3] Davies IW, Gerena L, Cai D, Larsen RD, Verhoeven TR, Reider PJ, Tetrahedron Lett., 38, 1145 (1997)

[4] Sundberg RJ, Pitts WJ, J. Org. Chem., 45, 3048 (1991)

[5] Ito K, Katsuki T, Tetrahedron Lett., 34, 2661 (1993)

[6] Sawamura M, Ito Y, Chem. Rev., 92, 857 (1992)

[7] Evans DA, Woerpel KA, Hinmal MM, Faul MM, J. Am. Chem. Soc., 113, 726 (1991)

[8] Bedekar AV, Andersson PG, Tetrahedron Lett., 37, 4073 (1996)

[9] Muller D, Umbricht G, Weber B, Pfaltz A, Helv. Chim. Acta, 74, 232 (1991)

[10] Lowenthal RE, Masamune S, Tetrahedron Lett., 32, 7373 (1991)

[11] Fraile JM, Garcia JI, Mayoral JA, Tarnal T, Tetrahedron: Asymmetry, 8, 2089 (1997)

[12] Leutenegger U, Umbricht G, Fahrni C, von Matt P, Pfaltz A, Tetrahedron, 48, 2143 (1992)

[13] Harm AM, Knight JG, Stemp G, Tetrahedron Lett., 37, 6189 (1996)

[14] Bedekar AV, Koroleva EB, Andersson PG, J. Org. Chem., 62, 2518 (1997)

[15] Fritschi H, Leutenegger U, Siegmann K, Pfaltz A, Helv. Chim. Acta, 71, 1541 (1988)

[16] Kanemasa S, Hamura S, Harada E, Yamamoto H, Tetrahedron Lett., 35, 7985 (1994)

[17] Kim HS, Kim JW, Kwon SC, Shim SC, Kim TJ, J. Org. Chem., 545 (1997)

[18] Vanveggel FC, Verboom W, Reinhoudt DN, Chem. Rev., 94(2), 279 (1994)

[19] Togni A, Breutel C, Schnyder A, Spindler F, Landert H, Tijani A, J. Am. Chem. Soc., 116(9), 4062 (1994)

[20] Cullen WR, Evans SV, Han NF, Trotter J, Inorg. Chem., 26, 514 (1987)

[21] Kim SG, Cho CW, Ahn KH, Tetrahedron: Asymmetry, 8, 1023 (1997)

[22] Benito A, Cano J, Manez RM, Soto J, Paya J, Lloret F, Julve M, Faus J, Marcos MD, Inorg. Chem., 32, 1197 (1993)

[23] Green J, Sinn E, Woodward S, Polyhedron, 12, 991 (1993)

[24] Nlate S, Herdtweck E, Blumel J, Fischer RA, J. Org. Chem., 97, 545 (1997)

[25] Ichiyanagi T, Shimizu M, Fujisawa T, Tetrahedron, 53, 9599 (1997)

[26] Doyle MP, Accounts Chem. Res., 19, 348 (1986)

[27] Uozumi Y, Kyota H, Kishi E, Kitayama K, Hayashi T, Tetrahedron, 7, 1603 (1996)