有机催化剂催化的不对称oxo-Michael/Mannich串联反应研究
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摘要
本文设计、合成了一系列新型多功能催化剂,并对其合成方法进行了研究。将这些催化剂用于催化水杨醛衍生的对甲苯磺酰亚胺与β-硝基苯乙烯的不对称oxo-Michael/Mannich串联反应,筛选出催化活性和对映选择性较好的多功能催化剂4b。并系统考察了反应溶剂、反应温度、催化剂量等因素对反应活性和选择性的影响,结果表明：反应以1,2-二氯乙烷作溶剂,10 mol%催化剂量,在-40℃下进行可获得85%的收率,e.e.值能达到87%,d.r.值高达99：1。
In this thesis, a series of novel multi-functional catalysts have been designed and synthesized, and their synthetic methodologies have also been studied. These multi-functional organocatalysts were further applied to catalyze the asymmetric oxo/Michael-Mannich domino reaction of salicyl N-tosylimine withβ-nitrostyrene. It was found that the multifunctional catalyst 4b could give good reactivity and enantioselectivity. The influences of reaction solvent, temperature, catalyst loading and etc on the reactivity and selectivity have been systematically investigated and the results have demonstrated that good yield (>85%), enantioselectivity (87% e.e.) and high diastereoselectivity (99:1 d.r.) were achieved when the reaction proceeded in 1,2 dichloroethane at-40℃with 10 mol% catalyst 4b.
In this thesis, a series of novel multi-functional catalysts have been designed and synthesized, and their synthetic methodologies have also been studied. These multi-functional organocatalysts were further applied to catalyze the asymmetric oxo/Michael-Mannich domino reaction of salicyl N-tosylimine withβ-nitrostyrene. It was found that the multifunctional catalyst 4b could give good reactivity and enantioselectivity. The influences of reaction solvent, temperature, catalyst loading and etc on the reactivity and selectivity have been systematically investigated and the results have demonstrated that good yield (>85%), enantioselectivity (87% e.e.) and high diastereoselectivity (99:1 d.r.) were achieved when the reaction proceeded in 1,2 dichloroethane at-40℃with 10 mol% catalyst 4b.
引文
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[43]Love, Brian E.; Raje, Prasad S; Williams Ⅱ, Thomas C. Synlett 1994,7,493-4.
[2]N. Halland, P. S.Aburel, K.A.J(?)rgensen,Angew. Chem.2004,116,1292
[3]J. Pulkkinen, P. S. Aburel, N. Hallend, K. A. Jorgensen, Adv. Synth. Catal.2004,346,1077-1080.
[4]D. Gryko, Tetrahedron:Asymmetry 2005,16,1377-1383.
[5]J.W. Yang, M. T. Hechavarria Fonsecca, B. List, J. Am. Chem. Soc.2005,127,15036-15037.
[6]Y. Huang, A. M. Walji, C. H. Larsen, D. W. C. MacMillan, J. Am. Chem. Soc.2005,127, 15051-15053.
[7]M. Marigo, T. Schulte, J. FranzQn, K. A. J(?)rgensen, J. Am. Chem.Soc. 2005,127,15710-15711.
[8]W. Wang, H. Li, J. Wang, L. Zu, J. Am. Chem. Soc.2006,128,10354-10355.
[9]T. Govender, L. Hojabri, F. M. Maghaddam, P. I. Arvidsson,Tetrahedron:Asymmetry,2006,17, 1763-4767.
[10]B.-C. Hong, M.-F.Wu, H.-C.Tseng, J.-H.Liao, Org. Lett.2006,8,2217-2220.
[11]Efraim Reyes, Garazi Talavera, Jose L.Vicario, Dolores Bada, and Luisa Carrillo,Angew. Chem. Int. Ed.2009,48,5701-5704.
[12]Sven Brandau, Eddy Maerten, Karl Anker J(?)rgensen,J. Am. Chem.Soc.2006,128,14986-14991
[13]R. K. Kunz, D.W. C. MacMillan, J. Am. Chem. Soc.2005,127,3240-3241.
[14]a) M. Marigo, J. FranzQn, T.B. Poulsen, W. Zhuang, K. A.J(?)rgensen, J. Am. Chem. Soc.2005, 127,6964-6965; b)W. Zhuang, M.Marigo, K. A. J(?)rgensen, Org. Biomol. Chem.2006,4, 3883-3385; c) H. Sunden, I. Ibrahem, A. Cordova, Tetrahedron Lett.2006,47,99-103.
[15]A. Cordova, W. Notz, C. F. Barbas Ⅲ, J. Org. Chem.2002,67,301-303.
[16]N. S. Chowdari, D. B. Ramachary, A. Cordova, C. F. Barbas III, Tetrahedron Lett.2002,43, 9591-9595.
[17]a) A. Cordova, Tetrahedron Lett.2004,45,3949-3952; b) J. Casas, M. Engquist, I. Ibrahem, B. Kaynak,A. Cordova, Angew. Chem.2005,117,1367-1369; c) A. Cordova, M. Engquist, I. Ibrahem, J.Casa, H. SundQn, Chem. Commun.2005,2047-2049; d) I. Ibrahem, A. Cordova, Tetrahedron Lett.2005,46,3363-3367; e) E. Reyes, A. Cordova, Tetrahedron Lett.2005,46, 6605-6609.
[18]N. S. Chowdari, D. B. Ramachary, C. F. Barbas Ⅲ, Org. Lett.2003,5,1685-2688.
[19]a) A. Bogevig, N.Kumaragurubaran, K. Juhl,W. Zhuang, K. A. Jorgensen, Angew.Chem.2002, 114,1868-187;b) N. Kumaragurubaran, K. Juhl, W. Zhuang, A. Bogevig, K. A.Jorgensen, J. Am. Chem. Soc.2002,124,6254-6255; c) B. List, J. Am.Chem. Soc.2002,124,5656-5657; d) H. Vogt, S. Vanderheiden, S.BrRse, Chem. Commun.2003,2448-2449. e) B. List, R. A.Lerner, C. F. Barbas Ⅲ, J. Am. Chem. Soc.2000,122,2395-2396; f)W.Notz, B. List, J. Am. Chem. Soc.2000. 122,7386-7387.
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[21]T. Itoh, M. Yokoya, K. Miyauchi, K. Nagata, A. Ohsawa, Org.Lett.2003,5,4301-4304.
[22]Y. Yamamoto, N. Momiyama, H. Yamamoto, J. Am. Chem. Soc.2004,126,5962-5963.
[23]H. SundQn, I. Ibrahem, L. Eriksen, A. Cordova, Angew. Chem.2005,117,4955-4958.
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[26]J. M. Betancort, K. Sakthivel, R. Thayumanavan, C. F. Barbas Ⅲ, Tetrahedron Lett.2001,42, 4441.4444
[27]D. B. Ramachary, N. S. Chowdari, C. F. Barbas Ⅲ, Angew.Chem.2003,115,4365-4369.
[28]a)D. B. Ramachary, C. F. Barbas Ⅲ, Chem. Eur. J.2004,10,5323-5531.b):D. B. Ramachary, K. Anebousely,N. S. Chowdary, C. F. Barbas Ⅲ, J. Org. Chem.2004,69,5838-5849.
[29]Bin Tan, Pei Juan Chua, Yongxin Li, and Guofu Zhong, Org. Lett.2008,10,2430-2440
[30]a) P. R. Schreiner, Chem. Soc. Rev.2003,32,289-296; b) P. M. Pihko, Angew. Chem.2004,116, 2110-2113; c) C. Bolm, T. Rantanen, I.Schiffers, L. Zani,Angew. Chem.2005,117,1788-1793; d) M. S. Taylor, E. N. Jacobsen, Angew.Chem.2006,118,1550-1573;e) T. Akiyama, J. Itoh, K. Fuchibe, Adv. Synth. Catal.2006,348,999-1010.
[31]Doyle A G, Jacobsen E N. Chem. Rev.2007,107,5713—5743
[32]a) Y. Hoashi, T. Yabuta, Y. Takemoto, Tetrahedron Lett.2004,45,9185-9188;b) Y. Hoashi, T. Yabuta, P. Yuan, H. Miyabe, Y.Takemoto, Tetrahedron 2006,62,365-374.
[33]Zhen-Xin Jia, Yong-Chun Luo, and Peng-Fei Xu,Org. Lett.2008,13,832-835
[34]Akiyama T. Chem. Rev.2007,107,5744—5758
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[37]Dorine Belmessieri, Louis C. Morrill, Carmen Simal, Alexandra M. Z. Slawin, and Andrew D. Smith, J. Am. Chem. Soc.2011,133,2714-2720
[38]Vakulya, Benedek; Varga, Szilard; Csampai, Antal; Soos, Tibor. Org. Lett.2005,7,1967-1969.
[39]Liu, Tian-Yu; Long, Jun; Li, Bang-Jing; Jiang, Lin; Li, Rui; Wu, Yong; Ding, Li-Sheng; Chen, Ying-Chun,Org. Biomol. Chem.2006,4,2097-2099.
[40]Sabot, Cyrille; Mosser, Michel; Antheaume, Cyril; Mioskowski, Charles; Baati, Rachid; Wagner, Alain. Chem. Commun.2009,23,3410-3412.
[41]Ye Zhu; Malerich, Jeremiah P.; Rawal, Viresh H. Angew. Chem.Int. Ed.2010,49,153-156,
[42](a)汪治,杨小生,郑安飘。化学通报,2002,89：557-559。(b)吴美芝,李晓如。江苏化工,2005,33(2)：35。
[43]Love, Brian E.; Raje, Prasad S; Williams Ⅱ, Thomas C. Synlett 1994,7,493-4.