Ir-catalysed asymmetric allylic substitutions with cyclometalated (phosphoramidite)Ir complexes - resting states, catalytically active (π-Allyl)Ir complexes and computational exploration

Chemistry - A European Journal

Volumn 16, Issue 22, 2010, Pages 6601-6615

  Raskatov, Jevgenij A ^a   Spiess, Stephanie ^a   Gnamm, Christian ^a   Brödner, Kerstin ^a   Rominger, Frank ^a   Helmchen, Günter ^a  

^a UNIVERSITY OF HEIDELBERG   (Germany)

Author keywords

Allylic compounds; Allylic substitution; Asymmetric catalysis; Iridium; Reaction mechanisms

Indexed keywords

ACTIVE CATALYST; ALLYL COMPLEXES; ALLYLIC COMPOUNDS; ALLYLIC SUBSTITUTION; ASYMMETRIC CATALYSIS; COMPUTATIONAL EXPLORATION; CYCLOMETALATION; CYCLOMETALATION PROCESS; DFT CALCULATION; IR COMPLEXES; IRIDIUM CATALYST; MECHANISTIC ASPECTS; NMR SPECTROSCOPY; OLEFIN COMPLEXES; ONE-POT PROCEDURES; PHOSPHORAMIDITES; REACTION MECHANISM; RESTING STATE; SPECTRAL DATA; TRANSITION STATE; X-RAY CRYSTAL STRUCTURE ANALYSIS;

CATALYSIS; CATALYSTS; CRYSTAL STRUCTURE; IRIDIUM; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; OLEFINS; SUBSTITUTION REACTIONS;

IRIDIUM COMPOUNDS;

EID: 77953170865     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200903465     Document Type: Article

References (53)

1. Reviews: a) G. Heimchen, A. Dahnz, P. Dubon, M. Schelwies, R. Weihofen, Chem. Commun. 2007, 675
2. b) G. Heimchen in Iridium Complexes in Organic Synthesis (Eds.: L. A. Oro, C. Claver), Wiley-VCH, Weinheim, 2009, pp. 211-250
3. c) R. Takeuchi, S. Kezuka, Synthesis 2006, 3349
4. d) H. Miyabe, Y. Takemoto, Synlett 2005, 1641.
5. C. Welter, O. Koch, G. Lipowsky, G. Helmchen, Chem. Commun. 2004, 896.
6. C. A. Kiener, C. Shu, C. Incarvito, J. F. Hartwig, J. Am. Chem. Soc. 2003, 125, 14272.
7. S. Spiess, C. Welter, G. Franck, J.-P. Taquet, G. Helmchen, Angew. Chem. 2008, 120, 7764
8. Angew. Chem. Int. Ed. 2008, 47, 7652.
9. R. Weihofen, O. Tverskoy, G. Helmchen, Angew. Chem. 2006, 118, 5673
10. Angew. Chem. Int. Ed. 2006, 45, 5546.
11. J. Tsuji, I. Minami, I. Shimizu, Tetrahedron Lett. 1984, 25, 5157.
12. DFT calculations have been carried out on chiral intermediates of Ir-catalysed allylic substitutions that have not been substantiated experimentally: a) N. Kinoshita, K. H. Marx, K. Tanaka, K. Tsubaki, T. Kawabata, N. Yoshikai, E. Nakamura, K. Fuji, J. Org. Chem. 2004, 69, 7960
13. b) M. Kimura, Y. Uozumi, J. Org. Chem. 2007, 72, 707.
14. S. Spiess, J. A. Raskatov, C. Gnamm, K. Brödner, G. Helmchen, Chem. Eur. J. 2009, 15, 11087.
15. a) D. Polet, A. Alexakis, K. Tissot-Croset, C. Corminboeuf, K. Ditrich, Chem. Eur. J. 2006, 12, 3596
16. b) K. Tissot-Croset, D. Polet, A. Alexakis, Angew. Chem. 2004, 116, 2480
17. Angew. Chem. Int. Ed. 2004, 43, 2426.
18. D. Markovid, J. F. Hartwig, J. Am. Chem. Soc. 2007, 129, 11680.
19. S. T. Madrahimov, D. Marković, J. F. Hartwig, J. Am. Chem. Soc. 2009, 131, 7228.
20. The complex K1H does not seem to affect further transformations. In the following the mixture of K1 and K1H as depicted in Figure 1A is designated K1.
21. 31PNMR spectroscopy; see the Supporting Information). For further experiments concerning this issue see the Supporting Information of reference [10].
22. 6 is formed (see, Scheme 3, lower left), which is stabilised by a Ph-→Ir coordination. See: T. Osswald, H. Rüegger, A. Mezzetti, Chem. Eur. J. 2010, 16, 1388.
23. We have earlier prepared and structurally characterised a (π-allyl)Ir complex with a PHOX ligand. Dimethyl malonate reacted with this complex at the central rather than the terminal allylic carbon, see C. Garcia-Yebra, J. P. Janssen, F. Rominger, G. Helmchen, Organometallics 2004, 23, 5459
24. for a (π-allyl)Ir complex containing a pybox ligand see P. Paredes, J. Díez, M. P. Gamusa, Organometallics 2008, 27, 2597.
25. Remarkably, crystals were only obtained if benzene was contained in the solvent, see reference [11].
26. T. Ohmura, J. F. Hartwig, J. Am. Chem. Soc. 2002, 124, 15164.
27. 31P NMR spectra did not change.
28. a) B. Bartels, C. Garcia-Yebra, G. Heimchen, Eur. J. Org. Chem. 2003, 1097
29. b) A. Leitner, C. Shu, J. F. Hartwig, Proc. Natl. Acad. Sci, USA 2004, 101, 5830.
30. M. J. Pouy, L. M. Stanley, J. F. Hartwig, J. Am. Chem. Soc. 2009, 131, 11312.
31. 2 group of the chiral ligand. The conformation of the chiral ligand backbone and the five-membered iridacycle were kept within the crystallographically determined conformation.
32. a) J. B. Wakefield, J.M. Stryker, J. Am. Chem. Soc. 1991, 113, 7057
33. b) E. B. Tjaden, K. E. Schwiebert, J. M. Stryker, J. Am. Chem. Soc. 1992, 114, 1100
34. c) E. B. Tjaden, J. M. Stryker, J. Am. Chem. Soc. 1990, 112, 6420.
35. A. D. Becke, J. Chem. Phys. 1993, 98, 1372
36. A. D. Becke, J. Chem. Phys. 1993, 98, 5648.
37. C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785.
38. Gaussian 03, Revision B.03, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian, Inc., Wallingford CT, 2004.
39. a) R. Ditchfield, W. J. Hehre, J. A. Pople, J. Chem. Phys. 1971, 54, 724
40. b) W. J. Hehre, R. Ditchfield, J. A. Pople, J. Chem. Phys. 1972, 56, 2257
41. c) P. C. Hariharan, J. A. Pople, Theo Chim. Ada 1973, 28, 213
42. d) P. C. Hariharan, J. A. Pople, Mol. Phys. 1974, 27, 209
43. e) M. S. Gordon, Chem. Phys. Lett 1980, 76, 163.
44. D. Andrae, U. Haeussermann, M. Dolg, H. Stoll, H. Preuss, Theor. Chim. Acta 1990, 77, 123.
45. C. Y. Peng, H. B. Schlegel, Isr. J. Chem. 1994, 34, 449.
46. C. Benzi, M. Cossi, V. Barone, R. Tarroni, C. Zannoni, J. Phys. Chem. B 2005, 109, 2584.
47. J. Tomasi, B. Mennucci, R. Cammi, Chem. Rev. 2005, 105, 2999.
48. H. E. Gottlieb, V. Kotylar, A. Nudelman, J. Org. Chem. 1997, 62, 7512.
49. S. Berger, Angew. Chem. 2004, 116, 2070.
50. SADABS 2008/1, G. M. Sheldrick, Bruker Analytical X-ray Division, Madison, Wisconsin 2008.
51. SHELXTL 2008/4, G. M. Sheldrick, Acta Crystallogr. Sect. A 2008, 64, 112.
52. C. Gnamm, G. Franck, N. Miller, T. Stork, K. Brödner, G. Helmchen, Synthesis 2008, 3331.
53. C. Gnamm, S. Förster, N. Miller, K. Brödner, G. Helmchen, Synlett 2007, 790.