SIOC English
化学学报
高级检索

化学学报 >

2012 , Vol. 70 >Issue 15: 1593 - 1598

DOI: https://doi.org/10.6023/A12060275

研究通讯

氮杂环卡宾双核金络合物催化的胺芳基化反应

  • 张睿 ,
  • 徐琴 ,
  • 施敏
展开
  • a 先进材料和精细化学品重点实验室 化学与分子工程学院 华东理工大学 上海 200237;
    b 金属有机化学国家重点实验室 中国科学院上海有机化学研究所 上海 200032

收稿日期: 2012-06-05

  网络出版日期: 2012-07-17

基金资助

项目受上海市科委(No. 11JC1402600)、中国国家基础研究项目(973)-(No. 2009CB825300)、中央高校基本科研业务费和国家自然科学基金(Nos. 21072206, 20472096, 20872162, 20672127, 21121062和20732008)资助.

收起

N-Heterocyclic Carbene (NHC) Binuclear Gold Complexes Catalyzed Aminoarylation of Olefins

  • Zhang Rui ,
  • Xu Qin ,
  • Shi Min
Expand
  • a Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China;
    b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China

Received date: 2012-06-05

  Online published: 2012-07-17

Supported by

Project supported by the Shanghai Municipal Committee of Science and Technology (No. 11JC1402600), National Basic Research Program of China (973)-(No. 2009CB825300), the Fundamental Research Funds for the Central Universities and the National Natural Science Foundation of China (Nos. 21072206, 20472096, 20872162, 20672127, 21121062 and 20732008).

Fold

摘要

联萘胺出发合成了氮杂环卡宾双核和单核金络合物, 通过X射线的单晶衍射确定了它们的结构, 并将其应用于催化胺芳基化反应中, 以高达95%的收率得到吡咯烷类化合物. 综合上述实验结果, 发现氮杂环卡宾双核金络合物4b中存在着Au(I)-Au(I)间相互弱作用力, 而且这种弱相互作用可能对该催化反应起重要的作用, 以高收率得到吡咯烷类化合物.

关键词： 联萘胺; 氮杂环卡宾; 金络合物; 金-金相互作用; 胺芳基化

本文引用格式

张睿 , 徐琴 , 施敏 . 氮杂环卡宾双核金络合物催化的胺芳基化反应[J]. 化学学报, 2012 , 70(15) : 1593 -1598 . DOI: 10.6023/A12060275

Abstract

N-Heterocyclic carbene (NHC) binuclear gold complexes and mononuclear gold complex have been successfully prepared from 1,1'-binaphthalenyl-2,2'-diamine (BINAM) in good yields. Their structures have been unambiguously determined by spectroscopic data and X-ray diffraction. On the basis of X-ray diffraction, a weak interaction between Au-Au has been identified in the N-heterocyclic carbene (NHC) binuclear gold complex 4b, in which the distance of Au(I)-Au(I) is 4.190 Å. We also found that NHC-binuclear gold complex 4b is a more effective catalyst than that of NHC-mononuclear gold complex in the aminoarylation of olefins under identical conditions. Based on these experimental data, the improved yield of aminoarylation is possibly attributed to the weak Au(I)-Au(I) interaction in the N-heterocyclic carbene (NHC) binuclear gold complex 4b. A plausible reaction mechanism has been proposed on the basis of previous literature. The reaction procedure is quite simple. When NHC-gold(I) catalyst 4b (3 mol%, 3.0 μmol) was dissolved in solvent (2.0 mL) in a flame-dried Schlenk tube equipped with a septum cap and stirring bar, the additive AgSbF6 (6.0 μmol) was added under argon, and then the mixture was stirred under argon at room temperature for 10 min. Alkylamine (0.1 mmol), arylboronic acid (0.2 mmol), and selectfluor (0.2 mmol) were added, and then the reaction mixture was stirred at 60 ℃ for 12 h. The crude product was concentrated under reduced pressure, and purified by flash chromatography on silica gel (eluent: EtOAc/petroleum ether＝1/16) to yield the pure corresponding product. Recently, a number of bis(gold) vinyl species have been isolated from homogeneous gold catalysis and have been identified as the key intermediate in the catalytic process. Meanwhile, binuclear gold complexes have been also realized as the key species in the homogeneous gold catalysis recently. In this paper, we first disclosed that the N-heterocyclic carbene (NHC) binuclear gold complex has a weak interaction between Au(I)-Au(I), which plays an important role in the aminoarylation of olefins.

Key words： BINAM; N-heterocyclic carbene; gold complex; gold(I)-gold(I) interaction; aminoarylation

参考文献

[1] Nicolaou, K. C.; Bulger, P. G.; Sarlah, D. Angew. Chem., Int. Ed. 2005, 44, 4442.



[2] Shapiro, N. D.; Toste, F. D. Synlett 2010, 675.



[3] Fürstner, A. Chem. Soc. Rev. 2009, 38, 3208.



[4] Jiménez-Núñez, E.; Echavarren, A. M. Chem. Rev. 2008, 108, 3326.



[5] Shen, H. C. Tetrahedron 2008, 64, 7847.



[6] Gorin, D. J.; Sherry, B. D.; Toste, F. D. Chem. Rev. 2008, 108, 3351.



[7] Li, Z.; Brouwer, C.; He, C. Chem. Rev. 2008, 108, 3239.



[8] Arcadi, A. Chem. Rev. 2008, 108, 3266.



[9] Hashmi, A. S. K. Chem. Rev. 2007, 107, 3180.



[10] Teles, J. H.; Brode, S.; Chabanas, M. Angew. Chem., Int. Ed. 1998, 37, 1415.



[11] Mizushima, E.; Sato, K.; Hayashi, T.; Tanaka, M. Angew. Chem., Int. Ed. 2002, 41, 4563.



[12] Reetz, M. T.; Sommer, K. Eur. J. Org. Chem. 2003, 3485.



[13] Mizushima, E.; Hayashi, T.; Tanaka, M. Org. Lett. 2003, 5, 3349.



[14] Nieto-Oberhuber, C.; Munuz, M. P.; Bunuel, E.; Nevado, C.; Cardenas, D. J.; Echavarren, A. M. Angew. Chem., Int. Ed. 2004, 43, 2403.



[15] Kennedy-Smith, J. J.; Staben, S. T.; Toste, F. D. J. Am. Chem. Soc. 2004, 126, 4526.



[16] Mamane, V.; Gress, T.; Krause, H.; Fürstner, A. J. Am. Chem. Soc. 2004, 126, 8654.



[17] Luzung, M. R.; Markham, J. P.; Toste, F. D. J. Am. Chem. Soc. 2004, 126, 10858.



[18] Hashmi, S. K.; Ramamurthi, T. D.; Rominger, F. J. Organomet. Chem. 2009, 694, 592.



[19] Zhang, G. Z.; Peng, Y.; Cui, L.; Zhang, L. Angew. Chem., Int. Ed. 2009, 48, 3112.



[20] Zhang, G. Z.; Cui, L.; Wang, Y. Z.; Zhang, L. J. Am. Chem. Soc. 2010, 132, 1474.



[21] Zhang, G.; Luo, Y.; Wang, Y.; Zhang, L. Angew. Chem., Int. Ed. 2011, 50, 4450.



[22] Melhado, A. D.; Brenzovich, W. E.; Lackner, A. D.; Toste, F. D. J. Am. Chem. Soc. 2010, 132, 8885.



[23] Brenzovich, W. E.; Benitez, D.; Lackner, A. D.; Shunatona, H. P.; Tkatchouk, E.; Goddard, W. A.; Toste, F. D. Angew. Chem., Int. Ed. 2010, 49, 5519.



[24] Mankad, N. P.; Toste, F. D. J. Am. Chem. Soc. 2010, 132, 12859.



[25] Brenzovich, W. E.; Brazeau, J. F.; Toste, F. D. Org. Lett. 2010, 12, 4728.



[26] Ball, L. T.; Green, M.; Lloyd-Jones, G. C.; Russel, C. A. Org. Lett. 2010, 12, 4724.



[27] Wang, W.; Jasinski, J.; Hammond, G. B.; Xu, B. Angew. Chem., Int. Ed. 2010, 49, 7247.



[28] Hopkinson, M. N.; Tessier, A.; Salisbury, A.; Giuffedi, G. T.; Combettes, L. E.; Gee, A. D.; Gouverneur, V. Chem. Eur. J. 2010, 16, 7443.



[29] de Haro, T.; Nevado, C. Angew. Chem., Int. Ed. 2011, 50, 906.



[30] Engle, K. M.; Mei, T.-S.; Wang, X.; Yu, J.-Q. Angew. Chem., Int. Ed. 2011, 50, 1478.



[31] Hopkins, M. N.; Gee, A. D.; Gouverneur, V. Chem. Eur. J. 2011, 30, 8248.



[32] Avdeef, A.; Fackler Jr,. J. P. Inorg. Chem. 1978, 17, 2182.



[33] Schmidbaur, H.; Schier, A. Chem. Soc. Rev. 2008, 37, 1931.



[34] Gimeno, M. C.; Laguna, A. Chem. Soc. Rev. 2008, 37, 1952.



[35] Tarselli, M. A.; Chianese, A. R.; Lee, S. J.; Gagné, M. R. Angew. Chem., Int. Ed. 2007, 46, 6670.



[36] Wang, M.-Z.; Zhou, C.-Y.; Guo, Z.; Wong, E. L.-M.; Wong, M.-K.; Che, C.-M. Chem. Asian J. 2011, 6, 812.



[37] Tkatchouk, E.; Mankad, N. P.; Benitez, D.; Goddard, W. A.; Toste, F. D. J. Am. Chem. Soc. 2011, 133, 14293.



[38] Lee, M.-T.; Hu, C.-H. Organometallics 2004, 23, 976.



[39] Huang, J.; Jafarpour, L.; Hillier, A. C.; Stevens, E. D.; Nolan, S. P. Organometallics 2001, 20, 2878.



[40] Bugaut, X.; Liu, F.; Glorius, F. J. Am. Chem. Soc. 2011, 133, 8130.



[41] Dabrowski, J. A.; Gao, F.; Hoveyda, A. H. J. Am. Chem. Soc. 2011, 133, 4778.



[42] Xiao, Y.-P.; Liu, X.-Y.; Che, C.-M. Angew. Chem., Int. Ed. 2011, 50, 4937.



[43] Xu, Q.; Duan, W.-L.; Lei, Z.-Y.; Zhu, Z.-B.; Shi, M. Tetrahedron 2005, 61, 11225.



[44] Chen, T.; Jiang, J.-J.; Xu, Q.; Shi, M. Org. Lett. 2007, 9, 865.



[45] Zhang, T.; Shi, M. Chem. Eur. J. 2008, 14, 3759-3764.



[46] Ma, G.-N.; Zhang, T.; Shi, M. Org. Lett. 2009, 11, 875-878.



[47] Wang, W.; Zhang, T.; Shi, M. Organometallics 2009, 28, 2640.



[48] Liu, Z.; Shi, M. Tetrahedron 2010, 66, 2619.



[49] Liu, Z.; Shi, M. Organometallics 2010, 29, 2831.



[50] Xu, Q.; Zhang, R.; Zhang, T.; Shi, M. J. Org. Chem. 2010, 75, 3935.



[51] Zhang, R.; Xu, Q.; Zhang, X.; Zhang, T.; Shi, M. Tetrahedron: Asymmetry 2010, 21, 1928.



[52] Wang, W.; Zhang, T.; Wang, F.; Shi, M. Tetrahedron 2011, 67, 1523.



[53] Liu, Z.; Gu, P.; Shi, M. Org. Lett. 2011, 13, 2314.



[54] Liu, Z.; Gu, P.; Shi, M. Chem. Eur. J. 2011, 17, 5796.



[55] Wang, W.; Yang, J.; Wang, F.; Shi, M. Organometallics 2011, 30, 3859.



[56] Zhang, R.; Xu, Q.; Mei, L.; Li, S.; Shi, M. Tetrahedron 2012, 68, 3172.



[57] Yang, J.; Zhang, R.; Wang, W.; Zhang, Z.; Shi, M. Tetrahedron: Asymmetry 2012, 22, 2029.



[58] The crystal data of 4b have been deposited in CCDC with number 870331. Empirical Formula: C48H34Au2Br2N4; Formula Weight: 1220.54; Crystal Color, Habit: colorless, Crystal Dimensions: 0.256×0.117×0.105 mm; Crystal System: Orthorhombic; Lattice Parameters: a＝10.2106(5) Å, b＝21.7203(11) Å, c＝23.1654(12) Å, α＝90°, β＝90°, γ＝90°, V＝5137.6(4) Å3; Space group: P2(1)2(1)2(1); Z＝4; Dcalc＝1.578 g/cm3; F000＝2312; Final R indices [I＞2σ(I)]: R1＝0. 0404; wR2＝0. 0977.



[59] The crystal data of 6 have been deposited in CCDC with number 877599. Empirical Formula: C36H27AuBrN3O; Formula Weight: 794.48; Crystal Color, Habit: colorless, Crystal Dimensions: 0.211×0.195×0.164 mm; Crystal System: Triclinic; Lattice Parameters: a＝9.1183(9) Å, b＝10.4649(10) Å, c＝15.5456(15) Å, α＝83.801(2)°, β＝79.355(2)°, γ＝86.758(2)°, V＝1448. 3(2) Å3; Space group: P-1; Z＝2; Dcalc＝1.822 g/cm3; F000＝772; Final R indices[I＞2σ(I)]: R1＝0.0462; wR2＝0.1140.
[60] Hu, S.-Z.; Zhou, Z.-H.; Cai, Q.-R. Acta Phys.-Chim. Sin. 2003, 19, 1073. (胡盛志, 周朝晖, 蔡启瑞, 物理化学学报, 2003, 19, 1073.)
Options
文章导航

/

〈 〉