Carbenes stabilized by ylides: Pushing the limits

Angewandte Chemie - International Edition

Volumn 47, Issue 43, 2008, Pages 8302-8306

  Fürstner, Alois ^a   Alcarazo, Manuel ^a   Radkowski, Karin ^a   Lehmann, Christian W ^a  

^a MAX PLANCK INSTITUT FÜR KOHLENFORSCHUNG   (Germany)

Author keywords

Carbenes; Heterocycles; Ligands; Rhodium; Ylides

Indexed keywords

AMINES; CHEMICAL REACTIONS; RHODIUM;

CARBENE; CARBENES; CARBON ATOMS; CHEMICAL EQUATIONS; ELECTRON DENSITIES; GAIN STABILITIES; HETEROCYCLES; REACTIVE INTERMEDIATES; YLIDES;

CHEMICAL STABILITY;

EID: 54249141380     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200803200     Document Type: Article

References (52)

1. Carbene Chemistry. From Fleeting Intermediates to Powerful Reagents (Ed.: G. Bertrand), Dekker, New York, 2002.
2. a) A. J. Arduengo, Acc. Chem. Res. 1999, 32, 913-921;
3. b) D. Bourissou, O. Guerret, F. P. Gabbaï, G. Bertrand, Chem. Rev. 2000, 100, 39-92;
4. c) W. A. Herrmann, Angew. Chem. 2002, 114, 1342-1363;
5. Angew. Chem. Int. Ed. 2002, 41, 1290-1309;
6. d) F. E. Hahn, M. C. Jahnke, Angew. Chem. 2008, 120, 3166-3216;
7. Angew. Chem. Int. Ed. 2008, 47, 3122-3172;
8. e) D. Enders, O. Niemeier, A. Henseler, Chem. Rev. 2007, 107, 5606-5655;
9. f) N-Heterocyclic Carbenes in Synthesis (Ed.: S. P. Nolan), Wiley-VCH, Weinheim, 2006.;
10. g) "N-Heterocyclic Carbenes in Transition Metal Catalysis": Topics in Organometic Chemistry, Vol. 21 (Ed.: F. Glorius), Springer, Berlin, 2007;
11. h) for an extensive literature coverage, see also: D. Kremzow, G. Seidel, C. W. Lehmann, A. Fürstner, Chem. Eur. J. 2005, 11, 1833-1853.
12. 2 followed by O-alkylation( silylation) of the resulting intermediates. However, all available spectroscopic and structural data show that these products must not be interpreted as (phosphorus ylide)carbene complexes I, but constitute phosphoniovinyl metal complexes II.
13. For pioneering studies, see the following and literature cited therein: a) W. C. Kaska, D. K. Mitchell, R. F. Reichelderfer, W. D. Korte, J. Am. Chem. Soc. 1974, 96, 2847-2854;
14. b) S. Voran, H. Blau, W. Malisch, U. Schubert, J. Organomet. Chem. 1982, 232, c33-c40;
15. c) N. E. Kolobova, L. L. Ivanov, O. S. Zhvanko, I. N. Chechulina, A. S. Batsanov, Y. T. Struchkov, J. Organomet. Chem. 1982, 238, 223-229;
16. d) W. Malisch, H. Blau, U. Schubert, Chem. Ber. 1983, 116, 690-709.
17. a) G. Facchin, R. Campostrini, R. A. Michelin, J. Organomet. Chem. 1985, 294, c21-c25;
18. b) R. A. Michelin, G. Facchin, D. Braga, P. Sabatino, Organometallics 1986, 5, 2265-2274;
19. c) R. A. Michelin, M. Mozzon, G. Facchin, D. Braga, P. Sabatino, J. Chem. Soc. Dalton Trans. 1988, 1803-1811;
20. d) G. Facchin, M. Mozzon, R. A. Michelin, M. T. A. Ribeiro, A. J. L. Pombeiro, J. Chem. Soc. Dalton Trans. 1992, 2827-2835;
21. e) M. Tamm, F. E. Hahn, Coord. Chem. Rev. 1999, 182, 175-209.
22. a) S. Nakafuji, J. Kobayashi, T. Kawashima, Angew. Chem. 2008, 120, 1157-1160;
23. Angew. Chem. Int. Ed. 2008, 47, 1141-1144;
24. b) for a recent extension to a pyrrole-based (amino)bis-(ylide)carbene, see: M. Asay, B. Donnadieu, A. Baceiredo, M. Soleilhavoup, G. Bertrand, Inorg. Chem. 2008, 47, 3949-3951.
25. In a formal sense, AYCs are a subtype of the cyclic (alkyl)aminocarbenes (CAACs), which are also strong donors, see: a) V. Lavallo, Y. Canac, C. Präsang, B. Donnadieu, G. Bertrand, Angew. Chem. 2005, 117, 5851-5855;
26. Angew. Chem. Int. Ed. 2005, 44, 5705-5709;
27. b) V. Lavallo, Y. Canac, A. DeHope, B. Donnadieu, G. Bertrand, Angew. Chem. 2005, 117, 7402-7405;
28. Angew. Chem. Int. Ed. 2005, 44, 7236-7239;
29. c) J. Vignolle, H. Gornitzka, B. Donnadieu, D. Bourissou, G. Bertrand, Angew. Chem. 2008, 120, 2303-2306;
30. Angew. Chem. Int. Ed. 2008, 47, 2271-2274;
31. d) V. Lavallo, G. D. Frey, B. Donnadieu, M. Soleilhavoup, G. Bertrand, Angew. Chem. 2008, 120, 5302-5306;
32. Angew. Chem. Int. Ed. 2008, 47, 5224-5228.
33. Prepared according to: K. Hartke, D. Teuber, H.-D. Gerber, Tetrahedron 1988, 44, 3261-3270.
34. The rather low yield is due, in part, to the limited stability of the complex during flash chromatography.
35. Anisotropic displacement parameters are drawn at the 50% probability level, hydrogen atoms have been omitted for clarity. CCDC 692803 (2), 692804 (3), 692800 (10a), 692801 (11), 692805 (14), and 692802 (20) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. The structure of 10a in the solid state as well as short summaries of the crystallographic data can be found in the Supporting Information of this paper.
36. Reference bond lengths: F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, A. G. Orpen, R. Taylor, J. Chem. Soc. Perkin Trans. 2 1987, S1-S19.
37. NHCs in free and complexed form are distinguished by small N-C-N angles, see Ref. [2] for pertinent reviews and the following for pioneering studies: a) A. J. Arduengo, R. L. Harlow, M. Kline, J. Am. Chem. Soc. 1991, 113, 361-363;
38. b) A. J. Arduengo, H. V. R. Dias, R. L. Harlow, M. Kline, J. Am. Chem. Soc. 1992, 114, 5530-5534;
39. c) A. J. Arduengo, F. Davidson, H. V. R. Dias, J. R. Goerlich, D. Khasnis, W. J. Marshall, T. K. Prakasha, J. Am. Chem. Soc. 1997, 119, 12742-12749;
40. d) for pertinent examples from our research group, see: A. Fürstner, H. Krause, L. Ackermann, C. W. Lehmann, Chem. Commun. 2001, 2240-2241;
41. e) A. Fürstner, L. Ackermann, B. Gabor, R. Goddard, C. W. Lehmann, R. Mynott, F. Stelzer, O. R. Thiel, Chem. Eur. J. 2001, 7, 3236-3253.
42. 2Cl], see: A. Fürstner, M. Alcarazo, H. Krause, C. W. Lehmann, J. Am. Chem. Soc. 2007, 129, 12 676-12677 and its Supporting Information .
43. R. Gompper, E. Kujath, H.-U. Wagner, Angew. Chem. 1982, 94, 559-560;
44. Angew. Chem. Int. Ed. Engl 1982, 21, 543-544.
45. Hydrazones 10 can, but need not, be isolated. For the structure of compound 10a in the solid state, see the Supporting Information.
46. 2 is best carried out under microwave irradiation. Under these conditions, the conversion of 9 into 11 a (R = Ph) can be performed in one pot.
47. D. Enders, K. Breuer, G. Raabe, J. Runsink, J. H. Teles, J.-P. Melder, K. Ebel, S. Brode, Angew. Chem. 1995, 107, 1119-1122;
48. Angew. Chem. Int. Ed. Engl. 1995, 34, 1021-1023.
49. A. Fürstner, M. Alcarazo, R. Goddard, C. W. Lehmann, Angew. Chem. 2008, 120, 3254-3258;
50. Angew. Chem. Int. Ed. 2008, 47, 3210-3214, and references therein.
51. Inspiration was provided by: a) N. A. Piro, J. S. Owen, J. E. Bercaw, Polyhedron 2004, 23, 2797-2804;
52. b) J. S. Owen, J. A. Labinger, J. E. Bercaw, J. Am. Chem. Soc. 2004, 126, 8247-8255.