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.
1 Introduction
2 Copper-Hydride-Mediated Reactions
2.1 Reduction of Carbonyl Compounds
2.1.1 Activity and Scope
2.1.2 Mechanistic Considerations
2.2 Related Transformations
3 Carbene Transfer Reactions
3.1 Cyclopropanation and Insertion Reactions
3.2 Olefination Reactions
4 [3+2] Cycloaddition of Azides and Alkynes
4.1 ‘Click Chemistry’
4.2 Use of Internal Alkynes: Mechanistic Implications
5 Miscellaneous Reactions
6 Concluding Remarks
Key words
N-heterocyclic carbene - copper - diazo compounds - homogeneous catalysis - hydrosilylation
References
1a </A>
Wanzlick H.-W.
Angew. Chem., Int. Ed. Engl.
1962,
1:
75 ; Angew. Chem. 1962 , 74 , 129
1b </A>
Wanzlick H.-W.
Esser F.
Kleiner H.-J.
Chem. Ber.
1963,
96:
1208
1c </A>
Wanzlick H.-W.
Schönherr H.-J.
Angew. Chem., Int. Ed. Engl.
1968,
7:
141
2a </A>
Öfele K.
J. Organomet. Chem.
1968,
12:
P42
2b </A>
Öfele K.
Angew. Chem., Int. Ed. Engl.
1970,
9:
739
2c </A>
Öfele K.
J. Organomet. Chem.
1970,
22:
C9
3a </A>
Arduengo AJ.
Harlow RL.
Kline M.
J. Am. Chem. Soc.
1991,
113:
361
3b </A>
Arduengo AJ.
Acc. Chem. Res.
1999,
32:
913
<A NAME="RA45507ST-4">4 </A>
Tolman CA.
Chem. Rev.
1997,
77:
313
5a </A>
Cavallo L.
Correa A.
Costabile C.
Jacobsen H.
J. Organomet. Chem.
2005,
690:
5407
5b </A>
Díez-González S.
Nolan SP.
Coord. Chem. Rev.
2007,
251:
874
<A NAME="RA45507ST-6">6 </A>
Marion N.
Díez-González S.
Nolan SP.
Angew. Chem. Int. Ed.
2007,
46:
2988
<A NAME="RA45507ST-7">7 </A>
Green JC.
Scur RG.
Arnold PL.
Cloke GN.
Chem. Commun.
1997,
1963
8a </A>
Peris E.
Crabtree RH.
Coord. Chem. Rev.
2004,
248:
2239
8b </A>
César V.
Bellemin-Laponnaz S.
Gade LH.
Chem. Soc. Rev.
2004,
33:
619
8c </A>
Díez-González S.
Nolan SP.
Annu. Rep. Prog. Chem., Sect. B: Org. Chem.
2005,
101:
171
8d </A>
Nolan SP.
N-Heterocyclic Carbenes in Synthesis
Wiley-VCH;
Weinheim:
2006.
8e </A>
Glorius F.
N-Heterocyclic Carbenes in Transition Metal Catalysis
Springer;
Berlin:
2007.
<A NAME="RA45507ST-9">9 </A>
Arduengo AJ.
Dias HVR.
Calabrese JC.
Davidson F.
Organometallics
1993,
12:
3405
10a </A>
Raubenheimer HG.
Cronje S.
van Rooyen PH.
Olivier PJ.
Toerien JG.
Angew. Chem., Int. Ed. Engl.
1994,
33:
672
10b </A>
Raubenheimer HG.
Cronje S.
Olivier PJ.
J. Chem. Soc., Dalton Trans.
1995,
313
11a </A>
Jurkauskas V.
Sadighi JP.
Buchwald SL.
Org. Lett.
2003,
5:
2417
11b </A>
Kaur H.
Zinn FK.
Stevens ED.
Nolan SP.
Organometallics
2004,
23:
1157
11c </A>
Díez-González S.
Kaur H.
Zinn FK.
Stevens ED.
Nolan SP.
J. Org. Chem.
2005,
70:
4784
11d </A>
Mankad NP.
Gray TG.
Laitar DS.
Sadighi JP.
Organometallics
2004,
23:
1191
<A NAME="RA45507ST-12">12 </A>
Ren H.
Zhao X.
Xu S.
Song H.
Wang B.
J. Organomet. Chem.
2006,
691:
4109
tert -butoxide complexes, see:
13a </A>
Mankad NP.
Laitar DS.
Sadighi JP.
Organometallics
2004,
23:
3369
13b </A>
Goj LA.
Blue ED.
Munro-Leighton C.
Gunnoe B.
Petersen JL.
Inorg. Chem.
2005,
44:
8647
<A NAME="RA45507ST-14">14 </A>
Laitar DS.
Müller P.
Sadighi JP.
J. Am. Chem. Soc.
2005,
127:
17196
<A NAME="RA45507ST-15">15 </A>
Welle A.
Díez-González S.
Tinant B.
Nolan SP.
Riant O.
Org. Lett.
2006,
8:
6059
<A NAME="RA45507ST-16">16 </A>
Wurtz A.
Ann. Chim. Phys.
1844,
11:
250
<A NAME="RA45507ST-17">17 </A>
Bezman SA.
Churchill MR.
Osborn JA.
Wormald J.
J. Am. Chem. Soc.
1971,
93:
2063
<A NAME="RA45507ST-18">18 </A>
Mahoney WS.
Brestensky DM.
Stryker JM.
J. Am. Chem. Soc.
1988,
110:
291
<A NAME="RA45507ST-19">19 </A>
Mahoney WS.
Stryker JM.
J. Am. Chem. Soc.
1989,
111:
8818
20a </A>
Lipshutz BH.
Keith J.
Papa P.
Vivian R.
Tetrahedron Lett.
1998,
39:
4627
20b </A>
Lipshutz BH.
Chrisman W.
Noson K.
Papa P.
Sclafani JA.
Vivian RW.
Keith JM.
Tetrahedron
2000,
56:
2779
21a </A>
Lipshutz BH.
Chrisman W.
Noson K.
J. Organomet. Chem.
2001,
624:
367
21b </A>
Lipshutz BH.
Caires CC.
Kuipers P.
Chrisman W.
Org. Lett.
2003,
5:
3085
22a </A>
Wishka DG.
Graber DR.
Seest EP.
Dolak FH.
Watt W.
Morris J.
J. Org. Chem.
1998,
63:
7851
22b </A>
Deeter J.
Frazier J.
Staten G.
Staszak M.
Weigel L.
Tetrahedron Lett.
1990,
31:
7101
22c </A>
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
<A NAME="RA45507ST-23">23 </A>
Bantu B.
Wang D.
Wurst K.
Buchmeiser MR.
Tetrahedron
2005,
61:
12145
<A NAME="RA45507ST-24">24 </A>
Lorenz C.
Schubert U.
Chem. Ber.
1995,
128:
1267
25a </A>
Pagenkopf BL.
Krüger J.
Stojanovic A.
Carreira EM.
Angew. Chem. Int. Ed.
1998,
37:
3124
25b </A>
See also ref. 22.
26a </A>
Moritami Y.
Appella DH.
Jurkauskas V.
Buchwald SL.
J. Am. Chem. Soc.
2000,
122:
6797
26b </A>
Yun J.
Buchwald SL.
Org. Lett.
2001,
3:
1129
27a </A>
Chiu P.
Chen B.
Cheng KF.
Tetrahedron Lett.
1998,
39:
9229
27b </A>
Chiu P.
Szeto C.-P.
Geng Z.
Cheng K.-F.
Org. Lett.
2001,
3:
1901
27c </A>
Chiu P.
Szeto CP.
Geng Z.
Cheng KF.
Tetrahedron Lett.
2001,
42:
4091
28a </A>
Chiu P.
Leung SK.
Chem. Commun.
2004,
2308
28b </A>
Chiu P.
Synthesis
2004,
2210
29a </A>
Lam HW.
Joensuu PM.
Org. Lett.
2005,
7:
4225
29b </A>
Deschamp J.
Chuzel O.
Hannedouche J.
Riant O.
Angew. Chem. Int. Ed.
2006,
45:
1292
29c </A>
Zhao DB.
Oisaki K.
Kanai M.
Shibasaki M.
Tetrahedron Lett.
2006,
47:
1403
29d </A>
Chuzel O.
Deschamp J.
Chausteur C.
Riant O.
Org. Lett.
2006,
8:
5943
<A NAME="RA45507ST-30">30 </A>
Deutsch C.
Lipshutz BH.
Krause N.
Angew. Chem. Int. Ed.
2007,
46:
1650
<A NAME="RA45507ST-31">31 </A>
Smith MB.
March J.
Advanced Organic Chemistry: Reactions, Mechanism, and Structure
5th ed.:
Wiley-Interscience;
New York:
2001.
<A NAME="RA45507ST-32">32 </A>
Doyle MP.
McKervey MA.
Ye T.
Modern Catalytic Methods for Organic Synthesis with Diazo Compounds
John Wiley & Sons;
New York:
1998.
<A NAME="RA45507ST-33">33 </A>
Fructos MR.
Belderrain TR.
Nicasio MC.
Nolan SP.
Kaur H.
Díaz-Requejo MM.
Pérez PJ.
J. Am. Chem. Soc.
2004,
126:
10846
<A NAME="RA45507ST-34">34 </A>
Formation of the homocoupling byproduct had occurred with the previously reported
copper(I) complexes, see ref. 32.
<A NAME="RA45507ST-35">35 </A>
Gawley RE.
Narayan S.
Chem. Commun.
2005,
5109
36a </A>
Tanner D.
Angew. Chem., Int. Ed. Engl.
1994,
33:
599
36b </A>
Díaz-Requejo MM.
Pérez PJ.
J. Organomet. Chem.
2001,
617:
110
36c </A>
Borriero C.
Cucciolito ME.
Panunzi A.
Ruffo F.
Tetrahedron: Asymmetry
2001,
12:
2467
<A NAME="RA45507ST-37">37 </A>
Trost BM.
Dong G.
J. Am. Chem. Soc.
2006,
128:
6054
<A NAME="RA45507ST-38">38 </A>
Kelly SE. In
Comprehensive Organic Synthesis
Vol. 1:
Trost BM.
Fleming I.
Schreiber SL.
Pergamon;
Oxford:
1991.
p.729
39a </A>
Fujimura O.
Honma T.
Tetrahedron Lett.
1998,
39:
625
39b </A>
Graban E.
Lemke FR.
Organometallics
2002,
21:
3823
39c </A>
Sun W.
Kuhn FE.
Appl. Catal., A
2005,
285:
163
39d </A>
Sun W.
Yu BS.
Kuhn FE.
Tetrahedron Lett.
2006,
47:
1993
40a </A>
Lebel H.
Paquet V.
Proulx C.
Angew. Chem. Int. Ed.
2001,
40:
2887
40b </A>
Grasa GA.
Moore Z.
Martin KL.
Stevens ED.
Nolan SP.
Paquet V.
Lebel H.
J. Organomet. Chem.
2002,
658:
126
40c </A>
Lebel H.
Paquet V.
Org. Lett.
2002,
4:
1671
40d </A>
Lebel H.
Guay D.
Paquet V.
Huard K.
Org. Lett.
2004,
6:
3047
40e </A>
Lebel H.
Paquet V.
J. Am. Chem. Soc.
2004,
126:
320
40f </A>
Paquet V.
Lebel H.
Synthesis
2005,
1901
41a </A>
Liao Y.
Huang YZ.
Tetrahedron Lett.
1990,
31:
5897
41b </A>
Zhou ZL.
Huang YZ.
Shi LL.
Tetrahedron
1993,
49:
6821
<A NAME="RA45507ST-42">42 </A>
Lebel H.
Davi M.
Díez-González S.
Nolan SP.
J. Org. Chem.
2007,
72:
144
<A NAME="RA45507ST-43">43 </A>
As representative examples, the formation of the products given in Table
[4
<A NAME="RA45507ST-44">44 </A>
Kolb HC.
Finn MG.
Sharpless KB.
Angew. Chem. Int. Ed.
2001,
40:
2004
45a </A>
Tornø CW.
Christensen C.
Meldal M.
J. Org. Chem.
2002,
67:
3057
45b </A>
Rostovtsev VV.
Green LG.
Fokin VV.
Sharpless KB.
Angew. Chem. Int. Ed.
2002,
41:
2596
46a </A>
Huisgen R.
Pure Appl. Chem.
1989,
61:
613
46b </A>
Padwa A. In
Comprehensive Organic Synthesis
Vol. 4:
Trost BM.
Pergamon;
Oxford:
1991.
p.1069-1109
46c </A>
Huisgen R. In 1,3-Dipolar Cycloaddition Chemistry
Padwa A.
Wiley;
New York:
1984.
p.1-176
47a </A>
Lutz J.-F.
Börner HG.
Weichenhan K.
Macromol. Rapid Commun.
2005,
26:
514
47b </A>
Chan TR.
Hilgraf R.
Sharpless KB.
Fokin VV.
Org. Lett.
2004,
6:
2853
47c </A>
Lewis WG.
Magallon FG.
Fokin VV.
Finn MG.
J. Am. Chem. Soc.
2004,
126:
9152
<A NAME="RA45507ST-48">48 </A>
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
<A NAME="RA45507ST-49">49 </A>
Gerard B.
Ryan J.
Beeler AB.
Porco JA.
Tetrahedron
2006,
62:
6405
50a </A>
Appukkuttan P.
Dehaen W.
Fokin VV.
Van der Rycken E.
Org. Lett.
2004,
6:
4223
50b </A>
Feldman AK.
Colasson B.
Fokin VV.
Org. Lett.
2004,
6:
3897
<A NAME="RA45507ST-51">51 </A>
Rodionov VO.
Fokin VV.
Finn MG.
Angew. Chem. Int. Ed.
2005,
44:
2210 ; see also ref. 45a
<A NAME="RA45507ST-52">52 </A>
Himo F.
Lovell T.
Hilgraf R.
Rostovtsev VV.
Noodleman L.
Sharpless KB.
Fokin VV.
J. Am. Chem. Soc.
2005,
127:
210
<A NAME="RA45507ST-53">53 </A>
Thompson JS.
Bradley AZ.
Park K.-H.
Dobbs KD.
Marshall W.
Organometallics
2006,
25:
2712
<A NAME="RA45507ST-54">54 </A>
Nolte C.
Mayer P.
Straub BF.
Angew. Chem. Int. Ed.
2007,
46:
2001
55a </A>
Tominaga S.
Oi Y.
Kato T.
An DK.
Okamoto S.
Tetrahedron Lett.
2004,
45:
5585
55b </A>
Okamoto S.
Tominaga S.
Saino N.
Kase K.
Shimoda K.
J. Organomet. Chem.
2005,
690:
6001
<A NAME="RA45507ST-56">56 </A>
Larsen AO.
Leu W.
Nieto Oberhuber C.
Campbell JE.
Hoveyda AH.
J. Am. Chem. Soc.
2004,
126:
11130
57a </A>
Alexakis A.
Winn CL.
Guillen F.
Pytkowicz J.
Roland S.
Mangeney P.
Adv. Synth. Catal.
2003,
345:
345
57b </A>
Clavier H.
Coutable L.
Guillemin J.-C.
Mauduit M.
Tetrahedron: Asymmetry
2005,
16:
921
57c </A>
Lee K.-s.
Brown MK.
Hird AW.
Hoveyda AH.
J. Am. Chem. Soc.
2006,
128:
7182
57d </A>
Martin D.
Kehrli S.
d’Augustin M.
Clavier H.
Mauduit M.
Alexakis A.
J. Am. Chem. Soc.
2006,
128:
8416
57e </A>
Brown MK.
May TL.
Baxter CA.
Hoveyda AH.
Angew. Chem. Int. Ed.
2007,
46:
1097
<A NAME="RA45507ST-58">58 </A>
Munro-Leighton C.
Blue ED.
Gunnoe TB.
J. Am. Chem. Soc.
2006,
128:
1446
<A NAME="RA45507ST-59">59 </A>
[(IPr)CuCl] is now commercially available from Strem.
