Stable Carbenes: From ‘Laboratory Curiosities’ to Catalysis Mainstays

Abstract

The past 20 years have witnessed an explosion in research in the area of stable carbenes. From laboratory curiosities, they have emerged as a front-line alternative to phosphines in metal catalysis. The range of reactivity that they enable in organocatalysis, much of it through their capability to render functional groups umpolung, is enviable. Of course, their unique properties enable them to outperform both phosphines and more traditional Lewis bases in specific transformations. This Cluster assembles leaders in the field that provide a brief introduction to the unique chemistry afforded by these species.

Key words

N-heterocyclic carbenes - organocatalysis - ligands on metal - asymmetric transformation

• References

• 1 Igau A, Grutzmacher H, Baceiredo A, Trinquier G, Betrand G. Angew. Chem. Int. Ed. 1989; 28: 621
• 2 Arduengo III AJ, Harlow RL, Kline M. J. Am. Chem. Soc. 1991; 113: 361
• 3a Ugai T, Dokawa T, Tsubokawa S. J. Pharm. Soc. Jpn. 1943; 63: 269
• 3b Breslow R. J. Am. Chem. Soc. 1958; 80: 3719
• 4 Sheehan JC, Hunnemann DH. J. Am. Chem. Soc 1966; 88: 3666
• 5a Wanzlick H.-W. Angew. Chem., Int. Ed. Engl. 1962; 1: 75
• 5b For a review of these ligands as phosphine mimics, see: Lappert MF. J. Organomet. Chem. 1988; 358: 185
• 6 Huang J, Stevens ED, Petersen JL, Nolan SP. J. Am. Chem. Soc. 1999; 121: 2674
• 7a Zhang C, Huang J, Trudell ML, Nolan SP. J. Org. Chem. 1999; 64: 3804
• 7b For well-defined Pd complexes, see: Viciu MS, Germaneau RF, Nolan SP. Org. Lett. 2002; 4: 4053
• 7c Marion N, Navarro O, Mei J, Stevens ED, Scott NM, Nolan SP. J. Am. Chem. Soc. 2006; 128: 4101
• 8 Enders D, Kallfass U. Angew. Chem. Int. Ed. 2002; 41: 1743
• 9 Kerr MS, Read de Alaniz J, Rovis T. J. Am. Chem. Soc. 2002; 124: 10298
• 10a Nyce GW, Lamboy JA, Connor EF, Waymouth RM, Hedrick JL. Org. Lett. 2002; 4: 3587
• 10b Grasa GA, Gueveli T, Singh R, Nolan SP. J. Org. Chem. 2003; 68: 2812
• 11a Chow KY.-K, Bode JW. J. Am. Chem. Soc. 2004; 126: 8126
• 11b Reynolds NT, Read de Alaniz J, Rovis T. J. Am. Chem. Soc. 2004; 126: 9518
• 12 Wallach O. Dtsch. Chem. Ges. 1873; 6: 114
• 13 Enders D, Breuer K, Raabe G, Runsink J, Teles JH, Melder J.-P, Ebel K, Brode S. Angew. Chem., Int. Ed. Engl. 1995; 34: 1021