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化学进展 2009, Vol. 21 Issue (6): 1229-1240 前一篇   后一篇

• 综述与评论 •

N-杂环卡宾及其金属络合物的合成*

姜岚1,2;李争宁2**;赵德峰1**   

  1. (1. 大连理工大学精细化工国家重点实验室 |大连 116012；2. 大连大学环境与化学工程学院 |辽宁省生物有机化学重点实验室  |大连 116622)
  • 收稿日期:2008-06-20 修回日期:2008-09-12 出版日期:2009-06-24 发布日期:2009-06-16
  • 通讯作者: 李争宁; 赵德峰 E-mail:znli@dl.cn; zhaodfg@sina.com
  • 基金资助:

    国家自然科学基金

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Synthesis of N-heterocyclic Carbenes and Metal Complexes

Jiang Lan1,2 ;  |Li Zhengning2** ;  |Zhao Defeng1**   

  1.  (1. State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116012, China;
    2. Liaoning Key Laboratory of Bioorganic Chemistry, College of Environment and Chemical Engineering, Dalian University, Dalian 116622, China）
  • Received:2008-06-20 Revised:2008-09-12 Online:2009-06-24 Published:2009-06-16
  • Contact: Li Zhengning; Zhao Defeng E-mail:znli@dl.cn; zhaodfg@sina.com

由于其强给电子能力、结构易修饰性和拓扑学特性，N-杂环卡宾成为继有机膦配体之后又一类重要的配体。其金属络合物在均相及不对称催化领域的催化性能是近期研究的热点，已有许多成功的结果。本文综述了近年来N-杂环卡宾及其金属络合物以及N-杂环卡宾的重要前体咪唑盐的合成方法。金属-N-杂环卡宾络合物的合成方法包括：(a)游离卡宾与金属化合物直接络合；(b)咪唑盐与金属化合物在强碱作用下络合；(c)利用Ag-NHC通过卡宾配体转移方法制备新的金属络合物。关于N-杂环卡宾前体的合成途径主要有：(a)乙二醛、伯胺和多聚甲醛的缩合反应；(b)卤代烷与咪唑及其取代咪唑的烷基化反应；(c)原甲酸酯与1,2-二胺的成环反应；(d)肼或酰胺与酸酐的环化反应；(e)用Na/K对环硫脲化合物的还原反应。

关键词： N-杂环卡宾, 金属-N-杂环卡宾络合物, 咪唑盐, 合成

Due to the strong electronic donor properties and the versatile structure which can be readily modified, as well as the distinct topography, N-heterocyclic carbene（NHC）is a new class of ligands as an alternative to traditional phosphine ones. Therefore, it is attractive to use NHC as ligand in catalysis. In fact, the catalytic properties of NHC-metal (NHC-M) complexes in homogeneous and asymmetric catalysis has been a focused research field and many successful results have been reported in recent years. In this paper, the syntheses of NHC, NHC-M complexes and their major precursor imidazolium salts are reviewed. The synthetic methods for NHC-M complexes include: (a) reaction of metal complexes with pre-formed NHC ligands; (b) reaction of metal complexes with NHC precursor such as imidazolium salts and a strong base; (c) interaction between metal halide and NHC-Ag complexes. For the synthesis of NHC precursors, there are also several routes: (a) condensation of glyoxal, amines and paraformaldehyde; (b) alkylation of imidazole or monosubstituted imidazole with alkyl halide; (c) annulation of ortho esters and 1,2-diamines; (d) ring closure of hydrazines or amides with acetic anhydride; (e) reduction of thiones with Na/K in THF.

Contents
1 Introduction
2 The classification and structure of NHC
3 Synthesis of NHC and their metal complexes
3.1 Synthesis of NHC
3.2 Synthesis of NHC-metal complexes
4 Synthesis of NHC precursors
4.1 Synthesis of imidazolium salts
4.2 Synthesis of imidazolinyllium salts
4.3 Synthesis of triazolium salts
4.4 Synthesis of benzoimidazolium salts
4.5 Synthesis of bis-NHC precursors
5 Epilogue

Key words: N-heterocyclic carbene (NHC), NHC-metal complexes, imidazolium salts, synthesis

中图分类号: 

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[ 1 ] 　Fischer E O , Maasbêl A. Angew. Chem. Int . Ed. Engl . , 1964 ,3 : 580 —581
[ 2 ] 　Wanzlick H W. Angew. Chem. Int . Ed. Engl . , 1962 , 1 : 75 —80
[ 3 ] 　Wanzlick H W, Schênherr H J . Angew. Chem. Int . Ed. Engl . ,1968 , 7 : 141 —142
[ 4 ] 　Öfele K. Angew. Chem. Int . Ed. Engl . , 1969 , 8 : 916 —917
[ 5 ] 　Öfele K. J . Organomet . Chem. , 1968 , 12 : 42 —43
[ 6 ] 　Arduengo A J , Harlow R L , Kline M. J . Am. Chem. Soc. , 1991 ,113 : 361 —363
[ 7 ] 　Herrmann WA. Angew. Chem. Int . Ed. , 2002 , 41 : 1290 —1309
[ 8 ] 　Perry M C , Burgess K. Tetrahedron : Asymm. , 2003 , 14 : 951 —961
[ 9 ] 　César V , Bellemin-Laponnaz S , Gade L H. Chem. Soc. Rev. ,2004 , 33 : 619 —636
[10 ] 　Garrison J C , Youngs WJ . Chem. Rev. , 2005 , 105 : 3978 —4008
[11 ] 　Enders D , Niemeier O , Henseler A. Chem. Rev. , 2007 , 107 :5606 —5655
[12 ] 　李林涛(Li L T) , 麻生明(Ma SM) . 有机化学(Chin. J . Org.Chem. ) , 2001 , 21 : 75 —81
[13 ] 　柳清湘(Liu Q X) , 李正名(Li Z M) . 化学通报(Chemistry) ,2004 , 10 : 715 —722
[14 ] 　孙小宇(Sun X Y) , 吴　(Wu J ) . 有机化学(Chin. J . Org.Chem. ) , 2006 , 26 : 745 —756
[15 ] 　Despagnet-Ayoub E , Grubbs R H. J . Am. Chem. Soc. , 2004 ,126 : 10198 —10199
[16 ] 　Despagnet-Ayoub E , Grubbs R H. Organometallics , 2005 , 24 :338 —340
[17 ] 　Alder R W, Blake M E , Bortolotti C , Bufali S , Butts C P , Linehan E , Oliva J M, Orpen A G, Quayle MJ . Chem. Commun. , 1999 ,241 —242
[18 ] 　Guillen F , Winn C L , Alexakis A. Tetrahedron : Asymm. , 2001 ,12 : 2083 —2086
[19 ] 　Scarborough C C , Popp B V , Guzei I A , Stahl S S. J . Organomet .Chem. , 2005 , 690 : 6143 —6155
[20 ] 　Enders D , Breuer K, Raabe G, Runsink J , Teles J H , Melder J P ,Eble K, Brode S. Angew. Chem. Int . Ed. Engl . , 1995 , 34 :1021 —1023
[21 ] 　Enders D , Breuer K, Runsink J , Teles J H. Liebigs Ann. , 1996 ,2019 —2028
[22 ] 　Nyce GW, Csihony S , Waymouth R M, Hedrick J L. Chem. Eur.J . , 2004 , 10 : 4073 —4079
[23 ] 　Hahn F E , Wittenbecher L , Boese R , Bløser D. Chem. Eur. J . ,1999 , 5 : 1931 —1935
[24 ] 　Hahn F E , Wittenbecher L , Van D L , Frêhlich R. Angew. Chem.Int . Ed. , 2000 , 39 : 541 —544
[25 ] 　Méry D , Aranzaes J R , Astruc D. J . Am. Chem. Soc. , 2006 ,128 : 5602 —5603
[26 ] 　Herrmann W A , Goossen L J , Artus G R J , Kêcher C.Organometallics , 1997 , 16 : 2472 —2477
[27 ] 　Herrmann WA , Kêcher C , Gooβen L J , Artus G R J . Chem. Eur.J . , 1996 , 2 : 1627 —1636
[28 ] 　Weskamp T, Schattermann W C , Spiegler M, Herrmann W A.Angew. Chem. Int . Ed. , 1998 , 37 : 2490 —2493
[29 ] 　Scholl M, Trnka TM, Morgan J P , Grubbs R H. Tetrahedron Lett . ,1999 , 40 : 2247 —2250
[30 ] 　Kaur H , Zinn F K, Stevens E D , Nolan S P. Organometallics ,2004 , 23 : 1157 —1160
[31 ] 　Perry M C , Cui X, Burgess K. Tetrahedron : Asymm. , 2002 , 13 :1969 —1972
[32 ] 　Bao W, Wang Z, Li Y. J . Org. Chem. , 2003 , 68 : 591 —593
[33 ] 　Winn C L , Guillen F , Pytkowicz J , Roland S , Mangeney P ,Alexakis A. J . Organomet . Chem. , 2005 , 690 : 5672 —5695
[34 ] 　Lee S , Hartwig J F. J . Am. Chem. Soc. , 2001 , 66 : 3402 —3415
[35 ] 　Liu J , Chen J , Zhao J , Zhao Y, Li L , Zhang H. Synthesis , 2003 ,17 : 2661 —2666
[36 ] 　Bonhé te P , Dias A P , Papageorgiou N , Kalyanasundaram K, Gr? tzel M. Inorg. Chem. , 1996 , 35 : 1168 —1178
[37 ] 　史成武(Shi C W) , 葛茜(Ge Q) , 邱治国(Qiu Z G) , 李兵(Li B) , 韩士奎(Han S K) . 物理化学学报(Acta Physico-Chimica Sinica) , 2007 , 23 : 1473 —1477
[38 ] 　Powell M T, Hou D R , Perry M C , Cui X, Burgess K. J . Am.Chem. Soc. , 2001 , 123 : 8878 —8879
[39 ] 　Gade L H , César V , Bellemin-Laponnaz S. Angew. Chem. Int .Ed. , 2004 , 43 : 1014 —1017
[40 ] 　Arnold P L , Rodden M, Davis KM, Scarisbrick A C , Blake A J ,Wilson C. Chem. Commun. , 2004 , 1612 —1613
[41 ] 　Arnold P L , Scarisbrick A C , Blake A J , Wilson C. Chem.Commun. , 2001 , 2340 —2341
[42 ] 　Arduengo A J , Goerlich J R , Marshall WJ . J . Am. Chem. Soc. ,1995 , 117 : 11027 —11028
[43 ] 　Arduengo A J , Krafczyk R , Schmutzler R. Tetrahedron , 1999 , 55 :14523 —14534
[44 ] 　Funk T W, Berlin J M, Grubbs R H. J . Am. Chem. Soc. , 2006 ,128 : 1840 —1846
[45 ] 　Jurˇcík V , Gilani M, Wilhelm R. Eur. J . Org. Chem. , 2006 ,5103 —5109
[46 ] 　Veldhuizen J J V , Garber S B , Kingsbury J S , Hoveyda A H. J .Am. Chem. Soc. , 2002 , 124 : 4954 —4955
[47 ] 　Larsen A O , Leu W, Oberhuber C N , Campbell J E , Hoveyda A H.J . Am. Chem. Soc. , 2004 , 126 : 11130 —11131
[48 ] 　Waltman A W, Grubbs R H. Organometallics , 2004 , 23 : 3105 —3107
[49 ] 　Clavier H , Coutable L , Guillemin J C , Mauduit M. Tetrahedron :Asymm. , 2005 , 16 : 921 —924
[50 ] 　Clavier H , Coutable L , Toupet L , Guillemin J C , Mauduit M. J .Organomet . Chem. , 2005 , 690 : 5237 —5254
[51 ] 　Enders D , Gielen H. J . Organomet . Chem. , 2001 , 617P618 : 70 —80
[52 ] 　Rivas F M, Riaz U , Giessert A , Smulik J A , Diver S T. Org.Lett . , 2001 , 3 : 2673 —2676
[53 ] 　Metallinos C , Barrett F B , Chaytor J L , Heska M E A. Org. Lett . ,2004 , 6 : 3641 —3644
[54 ] 　Clyne D S , Jin J , Genest E , Gallucci J C , Rajanbabu T V. Org.Lett . , 2000 , 2 : 1125 —1128
[55 ] 　Duan W L , Shi M, Rong G B. Chem. Commun. , 2003 , 2916 —2917
[56 ] 　Chen T, Liu X G, Shi M. Tetrahedron , 2007 , 63 : 4874 —4880
[57 ] 　Bonnet L G, Douthwaite R E , Hodgson R. Organometallics , 2003 ,22 : 4384 —4386
[58 ] 　Douthwaite R E. Coord. Chem. Rev. , 2007 , 251 : 702 —717
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