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DOI: 10.1055/s-2007-985577
N-Heterocyclic Carbene-Copper(I) Complexes in Homogeneous Catalysis
Publikationsverlauf
Publikationsdatum:
13. August 2007 (online)
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Abstract
N-Heterocyclic carbenes (NHCs) have become increasingly popular as ligands for transition metals, thanks to their remarkable successes in metathesis and cross-coupling areas. Important advances have also been achieved in organocopper chemistry. To date, the reported neutral N-heterocyclic carbene-copper(I) complexes have shown outstanding catalytic activity. In this account, we describe the application of such complexes in a variety of organic transformations.
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1 Introduction
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2 Copper-Hydride-Mediated Reactions
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2.1 Reduction of Carbonyl Compounds
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2.1.1 Activity and Scope
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2.1.2 Mechanistic Considerations
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2.2 Related Transformations
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3 Carbene Transfer Reactions
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3.1 Cyclopropanation and Insertion Reactions
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3.2 Olefination Reactions
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4 [3+2] Cycloaddition of Azides and Alkynes
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4.1 ‘Click Chemistry’
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4.2 Use of Internal Alkynes: Mechanistic Implications
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5 Miscellaneous Reactions
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6 Concluding Remarks
Key words
N-heterocyclic carbene - copper - diazo compounds - homogeneous catalysis - hydrosilylation
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1a
Wanzlick H.-W. Angew. Chem., Int. Ed. Engl. 1962, 1: 75 ; Angew. Chem. 1962, 74, 129 -
1b
Wanzlick H.-W.Esser F.Kleiner H.-J. Chem. Ber. 1963, 96: 1208 -
1c
Wanzlick H.-W.Schönherr H.-J. Angew. Chem., Int. Ed. Engl. 1968, 7: 141 -
2a
Öfele K. J. Organomet. Chem. 1968, 12: P42 -
2b
Öfele K. Angew. Chem., Int. Ed. Engl. 1970, 9: 739 -
2c
Öfele K. J. Organomet. Chem. 1970, 22: C9 -
3a
Arduengo AJ.Harlow RL.Kline M. J. Am. Chem. Soc. 1991, 113: 361 -
3b
Arduengo AJ. Acc. Chem. Res. 1999, 32: 913 - 4
Tolman CA. Chem. Rev. 1997, 77: 313 -
5a
Cavallo L.Correa A.Costabile C.Jacobsen H. J. Organomet. Chem. 2005, 690: 5407 -
5b
Díez-González S.Nolan SP. Coord. Chem. Rev. 2007, 251: 874 - 6
Marion N.Díez-González S.Nolan SP. Angew. Chem. Int. Ed. 2007, 46: 2988 - 7
Green JC.Scur RG.Arnold PL.Cloke GN. Chem. Commun. 1997, 1963 -
8a
Peris E.Crabtree RH. Coord. Chem. Rev. 2004, 248: 2239 -
8b
César V.Bellemin-Laponnaz S.Gade LH. Chem. Soc. Rev. 2004, 33: 619 -
8c
Díez-González S.Nolan SP. Annu. Rep. Prog. Chem., Sect. B: Org. Chem. 2005, 101: 171 -
8d
Nolan SP. N-Heterocyclic Carbenes in Synthesis Wiley-VCH; Weinheim: 2006. -
8e
Glorius F. N-Heterocyclic Carbenes in Transition Metal Catalysis Springer; Berlin: 2007. - 9
Arduengo AJ.Dias HVR.Calabrese JC.Davidson F. Organometallics 1993, 12: 3405 -
10a
Raubenheimer HG.Cronje S.van Rooyen PH.Olivier PJ.Toerien JG. Angew. Chem., Int. Ed. Engl. 1994, 33: 672 -
10b
Raubenheimer HG.Cronje S.Olivier PJ. J. Chem. Soc., Dalton Trans. 1995, 313 - For representative examples of copper-halogen complexes, see:
-
11a
Jurkauskas V.Sadighi JP.Buchwald SL. Org. Lett. 2003, 5: 2417 -
11b
Kaur H.Zinn FK.Stevens ED.Nolan SP. Organometallics 2004, 23: 1157 -
11c
Díez-González S.Kaur H.Zinn FK.Stevens ED.Nolan SP. J. Org. Chem. 2005, 70: 4784 - For copper acetate complexes, see:
-
11d
Mankad NP.Gray TG.Laitar DS.Sadighi JP. Organometallics 2004, 23: 1191 - 12
Ren H.Zhao X.Xu S.Song H.Wang B. J. Organomet. Chem. 2006, 691: 4109 - For copper tert-butoxide complexes, see:
-
13a
Mankad NP.Laitar DS.Sadighi JP. Organometallics 2004, 23: 3369 - For copper ethoxide and phenoxide complexes, see:
-
13b
Goj LA.Blue ED.Munro-Leighton C.Gunnoe B.Petersen JL. Inorg. Chem. 2005, 44: 8647 - 14
Laitar DS.Müller P.Sadighi JP. J. Am. Chem. Soc. 2005, 127: 17196 - 15
Welle A.Díez-González S.Tinant B.Nolan SP.Riant O. Org. Lett. 2006, 8: 6059 - 16
Wurtz A. Ann. Chim. Phys. 1844, 11: 250 - 17
Bezman SA.Churchill MR.Osborn JA.Wormald J. J. Am. Chem. Soc. 1971, 93: 2063 - 18
Mahoney WS.Brestensky DM.Stryker JM. J. Am. Chem. Soc. 1988, 110: 291 - 19
Mahoney WS.Stryker JM. J. Am. Chem. Soc. 1989, 111: 8818 -
20a
Lipshutz BH.Keith J.Papa P.Vivian R. Tetrahedron Lett. 1998, 39: 4627 -
20b
Lipshutz BH.Chrisman W.Noson K.Papa P.Sclafani JA.Vivian RW.Keith JM. Tetrahedron 2000, 56: 2779 -
21a
Lipshutz BH.Chrisman W.Noson K. J. Organomet. Chem. 2001, 624: 367 -
21b
Lipshutz BH.Caires CC.Kuipers P.Chrisman W. Org. Lett. 2003, 5: 3085 -
22a
Wishka DG.Graber DR.Seest EP.Dolak FH.Watt W.Morris J. J. Org. Chem. 1998, 63: 7851 -
22b
Deeter J.Frazier J.Staten G.Staszak M.Weigel L. Tetrahedron Lett. 1990, 31: 7101 -
22c
Labelle M.Belley M.Gareau Y.Gauthier JY.Guay D.Gordon R.Grossman SG.Jones TR.Leblanc Y.McAuliffe M.McFarlane C.Masson P.Metters KM.Ouimet N.Patrick DH.Piechuta H.Rochette C.Sawyer N.Xiang YB.Pickett CB.Ford-Hutchinson AW.Zamboni RJ.Young RN. Bioorg. Med. Chem. Lett. 1995, 5: 283 - 23
Bantu B.Wang D.Wurst K.Buchmeiser MR. Tetrahedron 2005, 61: 12145 - 24
Lorenz C.Schubert U. Chem. Ber. 1995, 128: 1267 -
25a
Pagenkopf BL.Krüger J.Stojanovic A.Carreira EM. Angew. Chem. Int. Ed. 1998, 37: 3124 -
25b
See also ref. 22.
-
26a
Moritami Y.Appella DH.Jurkauskas V.Buchwald SL. J. Am. Chem. Soc. 2000, 122: 6797 -
26b
Yun J.Buchwald SL. Org. Lett. 2001, 3: 1129 -
27a
Chiu P.Chen B.Cheng KF. Tetrahedron Lett. 1998, 39: 9229 -
27b
Chiu P.Szeto C.-P.Geng Z.Cheng K.-F. Org. Lett. 2001, 3: 1901 -
27c
Chiu P.Szeto CP.Geng Z.Cheng KF. Tetrahedron Lett. 2001, 42: 4091 -
28a
Chiu P.Leung SK. Chem. Commun. 2004, 2308 -
28b
Chiu P. Synthesis 2004, 2210 -
29a
Lam HW.Joensuu PM. Org. Lett. 2005, 7: 4225 -
29b
Deschamp J.Chuzel O.Hannedouche J.Riant O. Angew. Chem. Int. Ed. 2006, 45: 1292 -
29c
Zhao DB.Oisaki K.Kanai M.Shibasaki M. Tetrahedron Lett. 2006, 47: 1403 -
29d
Chuzel O.Deschamp J.Chausteur C.Riant O. Org. Lett. 2006, 8: 5943 - 30
Deutsch C.Lipshutz BH.Krause N. Angew. Chem. Int. Ed. 2007, 46: 1650 - 31
Smith MB.March J. Advanced Organic Chemistry: Reactions, Mechanism, and Structure 5th ed.: Wiley-Interscience; New York: 2001. - 32
Doyle MP.McKervey MA.Ye T. Modern Catalytic Methods for Organic Synthesis with Diazo Compounds John Wiley & Sons; New York: 1998. - 33
Fructos MR.Belderrain TR.Nicasio MC.Nolan SP.Kaur H.Díaz-Requejo MM.Pérez PJ. J. Am. Chem. Soc. 2004, 126: 10846 - 35
Gawley RE.Narayan S. Chem. Commun. 2005, 5109 -
36a
Tanner D. Angew. Chem., Int. Ed. Engl. 1994, 33: 599 -
36b
Díaz-Requejo MM.Pérez PJ. J. Organomet. Chem. 2001, 617: 110 -
36c
Borriero C.Cucciolito ME.Panunzi A.Ruffo F. Tetrahedron: Asymmetry 2001, 12: 2467 - 37
Trost BM.Dong G. J. Am. Chem. Soc. 2006, 128: 6054 - 38
Kelly SE. In Comprehensive Organic Synthesis Vol. 1:Trost BM.Fleming I.Schreiber SL. Pergamon; Oxford: 1991. p.729 -
39a
Fujimura O.Honma T. Tetrahedron Lett. 1998, 39: 625 -
39b
Graban E.Lemke FR. Organometallics 2002, 21: 3823 -
39c
Sun W.Kuhn FE. Appl. Catal., A 2005, 285: 163 -
39d
Sun W.Yu BS.Kuhn FE. Tetrahedron Lett. 2006, 47: 1993 -
40a
Lebel H.Paquet V.Proulx C. Angew. Chem. Int. Ed. 2001, 40: 2887 -
40b
Grasa GA.Moore Z.Martin KL.Stevens ED.Nolan SP.Paquet V.Lebel H. J. Organomet. Chem. 2002, 658: 126 -
40c
Lebel H.Paquet V. Org. Lett. 2002, 4: 1671 -
40d
Lebel H.Guay D.Paquet V.Huard K. Org. Lett. 2004, 6: 3047 -
40e
Lebel H.Paquet V. J. Am. Chem. Soc. 2004, 126: 320 -
40f
Paquet V.Lebel H. Synthesis 2005, 1901 -
41a
Liao Y.Huang YZ. Tetrahedron Lett. 1990, 31: 5897 -
41b
Zhou ZL.Huang YZ.Shi LL. Tetrahedron 1993, 49: 6821 - 42
Lebel H.Davi M.Díez-González S.Nolan SP. J. Org. Chem. 2007, 72: 144 - 44
Kolb HC.Finn MG.Sharpless KB. Angew. Chem. Int. Ed. 2001, 40: 2004 -
45a
Tornø CW.Christensen C.Meldal M. J. Org. Chem. 2002, 67: 3057 -
45b
Rostovtsev VV.Green LG.Fokin VV.Sharpless KB. Angew. Chem. Int. Ed. 2002, 41: 2596 -
46a
Huisgen R. Pure Appl. Chem. 1989, 61: 613 -
46b
Padwa A. In Comprehensive Organic Synthesis Vol. 4:Trost BM. Pergamon; Oxford: 1991. p.1069-1109 -
46c
Huisgen R. In 1,3-Dipolar Cycloaddition ChemistryPadwa A. Wiley; New York: 1984. p.1-176 -
47a
Lutz J.-F.Börner HG.Weichenhan K. Macromol. Rapid Commun. 2005, 26: 514 -
47b
Chan TR.Hilgraf R.Sharpless KB.Fokin VV. Org. Lett. 2004, 6: 2853 -
47c
Lewis WG.Magallon FG.Fokin VV.Finn MG. J. Am. Chem. Soc. 2004, 126: 9152 - 48
Pérez-Balderas F.Ortega-Muñoz M.Morales-Sanfrutos J.Hernández-Mateo F.Calvo-Flores FG.Calvo-Asín JA.Isac-García J.Santoyo-González F. Org. Lett. 2003, 5: 1951 - 49
Gerard B.Ryan J.Beeler AB.Porco JA. Tetrahedron 2006, 62: 6405 - For previously reported systems, see:
-
50a
Appukkuttan P.Dehaen W.Fokin VV.Van der Rycken E. Org. Lett. 2004, 6: 4223 -
50b
Feldman AK.Colasson B.Fokin VV. Org. Lett. 2004, 6: 3897 - 51
Rodionov VO.Fokin VV.Finn MG. Angew. Chem. Int. Ed. 2005, 44: 2210 ; see also ref. 45a - 52
Himo F.Lovell T.Hilgraf R.Rostovtsev VV.Noodleman L.Sharpless KB.Fokin VV. J. Am. Chem. Soc. 2005, 127: 210 - 53
Thompson JS.Bradley AZ.Park K.-H.Dobbs KD.Marshall W. Organometallics 2006, 25: 2712 - 54
Nolte C.Mayer P.Straub BF. Angew. Chem. Int. Ed. 2007, 46: 2001 -
55a
Tominaga S.Oi Y.Kato T.An DK.Okamoto S. Tetrahedron Lett. 2004, 45: 5585 -
55b
Okamoto S.Tominaga S.Saino N.Kase K.Shimoda K. J. Organomet. Chem. 2005, 690: 6001 - 56
Larsen AO.Leu W.Nieto Oberhuber C.Campbell JE.Hoveyda AH. J. Am. Chem. Soc. 2004, 126: 11130 - For selected examples, see:
-
57a
Alexakis A.Winn CL.Guillen F.Pytkowicz J.Roland S.Mangeney P. Adv. Synth. Catal. 2003, 345: 345 -
57b
Clavier H.Coutable L.Guillemin J.-C.Mauduit M. Tetrahedron: Asymmetry 2005, 16: 921 -
57c
Lee K.-s.Brown MK.Hird AW.Hoveyda AH. J. Am. Chem. Soc. 2006, 128: 7182 -
57d
Martin D.Kehrli S.d’Augustin M.Clavier H.Mauduit M.Alexakis A. J. Am. Chem. Soc. 2006, 128: 8416 -
57e
Brown MK.May TL.Baxter CA.Hoveyda AH. Angew. Chem. Int. Ed. 2007, 46: 1097 - 58
Munro-Leighton C.Blue ED.Gunnoe TB. J. Am. Chem. Soc. 2006, 128: 1446
References
Formation of the homocoupling byproduct had occurred with the previously reported copper(I) complexes, see ref. 32.
43As representative examples, the formation of the products given in Table [4] , entries 1 and 4, was not observed when the reaction was carried out in the presence of copper(I) chloride instead of [(IPr)CuCl].
59[(IPr)CuCl] is now commercially available from Strem.