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Progress in Chemistry 2010, Vol. 22 Issue (10): 1964-1972 Previous Articles   Next Articles

• Review •

Cyanation Reactions with Potassium Hexacyanoferrate(II)

Wang Lili  Zhao Weining  Duan Zheng**   

  1. (Chemistry Department, Zhengzhou University, Zhengzhou 450001, China)
  • Received: Revised: Online: Published:
  • Contact: Duan Zheng E-mail:duanzheng@zzu.edu.cn
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Aryl nitriles are important building blocks in modern organic chemistry. They are integral parts of dyes, natural products, materials and agrochemicals. Many transition metals catalyzed or mediated displacements of aromatic halides by the cyanide ion have been developed. The traditional cyanide ion sources are KCN, NaCN, ZnCN, CuCN, (CH3)2C(OH)CN and TMSCN. But these cyanide sources have severe drawbacks: KCN and NaCN are highly poisonous, ZnCN2 and CuCN lead to stoichiometric amounts of heavy metal salt wastes, TMSCN and (CH3)2C(OH)CN are sensitive to moisture. In 2004, Prof. Beller and co-workers described for the first time the use of potassium hexacyanoferrate(II) (K4[Fe(CN)6]) as cyanating agent for the general synthesis of aryl nitriles from aryl bromides. They also found that all the six cyanide ions bound to the iron(II) center are used in the cyanation reaction. Compared with traditional cyanation reagents, potassium hexacyanoferrate(II) is nontoxic and can be handled without special precautions. Various methods for the synthesis of aryl nitriles with this user-friendly cyanating reagent have been developed. Very recently, direct cyanation reactions through transition-metal catalyzed C-H bond activation were reported. This review present the recent development of Pd and Cu catalyzed cyanation reactions with nontoxic and user-friendly potassium hexacyanoferrate(II) as the cyanating reagent.

Contents
1 Introduction
2 Palladium catalyzed cyanation reactions with potassium hexacyanoferrate(II)
3 Copper catalyzed cyanation reactions with potassium hexacyanoferrate(II)
4 Conclusions and outlook

[1 ] Larock R C. Comprehensive Organic Transformations: A Guide
to Functional Group Preparation. New York: VCH,1989. 819—
995
[2 ] Rappoport Z. Chemistry of the Cyano Group. London: John
Wiley & Sons,1970. 121—312
[3 ] Rosenmund K W,Struck E. Ber. Dtsch. Chem. Ges. ,1919,
52B: 1749—1756
[4 ] Braun J,Manz G. Anna. Chem. ,1931,488: 111—126
[5 ] Koelsch C F,Whitney A G. J. Org. Chem. ,1941,6: 795—
803
[6 ] Lindley J. Tetrahedron,1984,40(9) : 1433—1456
[7 ] Sandmeyer T. Ber. Dtsch. Chem. Ges. ,1884,17: 1633—
1635
[8 ] Hodgson H H. Chem. Rev. ,1947,40(2) : 251—277
[9 ] Galli C. Chem. Rev. ,1988,88(5) : 765—792
[10] Hanson P,Jones J R,Gilbert B C,Timms A W. J. Chem.
Soc. ,1991,7: 1009—1017
[11] Stevenson A C. Ind. Eng. Chem. ,1949,41: 1846—1851
[12] Denton W I,Bishop R B,Caldwell H P,Chapman H D. Ind.
Eng. Chem. ,1950,42: 796—800
[13] Martin A,Kalevaru N V,Lucke B,Sans J. Green Chem. ,
2002,4(5) : 481—485
[14] Takagi K,Okamoto T,Sakakibara Y,Oka S. Chem. Lett. ,
1973,5: 471—474
[15] Sundermeier M,Zapf A,Beller M. Eur. J. Inorg. Chem. ,
2003,19: 3513—3526
[16] Sakakibara Y,Okuda F,Shimobayashi A,Kirino K,Sakai M,
Uchino N,Takagi K. Bull. Chem. Soc. Jpn. ,1988,61 ( 6 ) :
1985—1990
[17] Brandsma L,Vasilevsky S F,Verkruijsse H D. Application ofTransition Metal Catalysts in Organic Synthesis. Berlin:
Springer,1998. 149—177
[18] Ellis G P,Romney-Alexander T M. Chem. Rev. ,1987,87
(4) : 779—794
[19] McMillen D F,Golden D M. Annu. Rev. Phys. Chem. ,1982,
33: 493—532
[20] Grushin V V,Alper H. Chem. Rev. ,1994,94 ( 4 ) : 1047—
1062
[21] Schareina T,Zapf A,Beller M. Chem. Commun. ,2004,12:
1388—1389
[22] Schareina T,Zapf A,Beller M. J. Organomet. Chem. ,2004,
689(24) : 4576—4583
[23] Weissman S A,Zewge D,Chen C. J. Org. Chem. ,2005,70
(4) : 1508—1510
[24] Grossman O,Gelman D. Org. Lett. ,2006,8(6) : 1189—1191
[25] Cheng Y N,Duan Z,Li T,Wu Y J. Lett. Org. Chem. ,2007,
4(5) : 352—356
[26] Cheng Y N,Duan Z,Li T,Wu Y J. Synlett,2007,4: 543—
546
[27] Schareina T, Zapf A, Mgerlein W, Müller N, Beller M.
Tetrahedron Lett. ,2007,48(7) : 1087—1090
[28] Schareina T,Jackstell R,Schulz T,Zapf A,Cotte A,Gotta M,
Beller M. Adv. Synth. Catal. ,2009,351(4) : 643—648
[29] Nandurkar N S,Bhanage B M. Tetrahedron,2008,64 ( 17 ) :
3655—3660
[30] Hassan J,Sévignon M,Gozzi C,Schulz E,Lemaire M. Chem.
Rev. ,2002,102(5) : 1359—1469
[31] Ren Y L,Liu Z F,He S B,Zhao S,Wang J J,Niu R Q,Yin
W P. Org. Process. Res. Dev. ,2009,13(4) : 764—768
[32] Zhu Y Z,Cai C. Synth. Commun. ,2007,37 ( 19 ) : 3359—
3366
[33] Zhu Y Z,Cai C. Eur. J. Org. Chem. ,2007,17: 2401—2404
[34] Polshettiwar V,Hesemann P,Moreau J J E. Tetrahedron,2007,
63(29) : 6784—6790
[35] Chattopadhyay K,Dey R,Ranu B C. Tetrahedron Lett. ,2009,
50(26) : 3164—3167
[36] Gedye R,Smith F,Westaway K,Ali H,Baldisera L,Laberge
L,Rousell J. Tetrahedron Lett. ,1986,27(3) : 279—282
[37] Gedye R N,Smith F E,Westaway K C. Can. J. Chem. ,1988,
66(1) : 17—26
[38] 金钦汉( Jin Q H) . 微波化学( Microwave Chemistry) . 北京:
科学出版社( Beijing: Science Press) ,1999. 126—147
[39] Wasserscheid P,Welton T. Ionic Liquids in Synthesis. 2nd ed.
Weinheim: Wiley-VCH,2008. 57—71
[40] Liao M C,Duan X H,Liang Y M. Tetrahedron Lett. ,2005,46
(20) : 3469—3472
[41] Wu J X,Beck B,Ren R X. Tetrahedron Lett. ,2002,43(3) :
387—389
[42] Li L H,Pan Z L,Duan X H,Liang Y M. Synlett,2006,13:
2094—2098
[43] Velmathi S,Leadbeate N E. Tetrahedron Lett. ,2008,49(32) :
4693—4694
[44] Chen G,Weng J,Zheng Z C,Zhu X H,Cai Y Y,Cai J W,
Wan Y Q. Eur. J. Org. Chem. ,2008,22: 3524—3528
[45] Takagi K,Sakakibara Y. Chem. Lett. ,1989,11: 1957—1958
[46] Srivastava R R,Zych A J,Jenkins D M,Wang H J,Chen Z J,
Fairfax D J. Synth. Commun. ,2007,37(3) : 431—438
[47] Uozumi Y, Suzuki N,Ogiwara A. Hayashi T. Tetrahedron,
1994,50(15) : 4293—4302
[48] Torrado M,Masa C F,Ravina E. Tetrahedron Lett. ,2007,48
(2) : 323—326
[49] Zhu Y Z,Cai C. Synth. Commun. ,2008,38 ( 16 ) : 2753—
2760
[50] Zhu Y Z,Cai C. Aust. J. Chem. ,2008,61(8) : 581—584
[51] Nakao Y,Yada A,Ebata S,Hiyama T. J. Am. Chem. Soc. ,
2007,129(9) : 2428—2429
[52] Wang C Y,Wang C,Wang Q F,Wang Z H,Sun H,Guo X Y,
Xi Z F. Chem. Eur. J. ,2007,13: 6484—6494
[53] Zhang H J,Meng T H,Demerseman B,Bruneau C,Xi Z F.
Org. Lett. ,2009,11(19) : 4458—4461
[54] Cheng Y N,Duan Z,Yu L J,Li Z X,Zhu Y,Wu Y J. Org.
Lett. ,2008,10(5) : 901—904
[55] Pinto A,Jia Y X,Neuville L,Zhu J P. Chem. Eur. J. ,2007,
13: 961—967
[56] Mariampillai B,Alliot J,Li M Z,Lautens M. J. Am. Chem.
Soc. ,2007,129(49) : 15372—15379
[57] Lu Z Y,Hu C M,Guo J J,Li J,Cui Y X,Jia Y X. Org.
Lett. ,2010,12(3) : 480—483
[58] Yan G B,Kuang C X,Zhang Y,Wang J B. Org. Lett. ,2010,
12(5) : 1052—1055
[59] Zanon J,Klapars A,Buchwald S L. J. Am. Chem. Soc. ,
2003,125(10) : 2890—2891
[60] Cristau H J,Ouali A,Spindler J F,Taillefer M. Chem. Eur.
J. ,2005,11: 2483—2492
[61] Schareina T,Zapf A,Beller M. Tetrahedron Lett. ,2005,46
(15) : 2585—2588
[62] Schareina T, Zapf A, Mgerlein W, Müller N, Beller M.
Synlett,2007,4: 555—558
[63] Schareina T,Zapf A,Mgerlein W,Müller N,Beller M. Chem.
Eur. J. ,2007,13: 6249—6254
[64] 蔡良珍( Cai L Z) ,刘斌( Liu B) ,董于虎( Dong Y H) ,杜广
延(Du G Y) ,陶晓春( Tao X C) . 化学学报( Acta Chimica
Sinica) ,2009,67(21) : 2523—2526
[65] Zhu Y Z,Cai C. J. Chem. Res. ,2007,8: 484—485
[66] Ren Y L,Liu Z F,Zhao S,Tian X Z,Wang J J,Yin W P,He
S B. Catal. Commun. ,2009,10(6) : 768—771
[67] Ren Y L,Zhao S,Cheng L,Tian X Z,Liu Z F. J. Mol. Catal.
( China) ,2009,23(5) : 387—391
[68] Ren Y L,Wang W,Zhao S,Tian X Z,Wang J J,Yin W P,
Cheng L. Tetrahedron Lett. ,2009,50(32) : 4595—4597
[69] DeBlase C, Leadbeater N E. Tetrahedron, 2010, 66 ( 5 ) :
1098—1101
[70] Li Z,Shi S Y,Yang J Y. Synlett,2006,15: 2495—2497
[71] 任运来(Ren R L) ,程林( Cheng L) ,刘志飞( Liu Z F) ,王伟
(Wang W) . 河南科技大学学报: 自然科学版( J. Henan
Univ. Science and Tech. : Natural Science) ,2009,30 ( 4 ) :
97—100
[72] Jia X F,Yang D P,Wang W H,Luo F,Cheng J. J. Org.
Chem. ,2009,74(24) : 9470—9474
[73] Franz A W,Popa L N,Müller T J J. Tetrahedron Lett. ,2008,
49(20) : 3300—3303

[1] Zhao Ping1,Yin Yingwu1,2**. Development of the Anodic Cyanation Reaction [J]. Progress in Chemistry, 2004, 16(06): 926-.