Regio- and enantioselective iridium-catalyzed allylic alkylation with in situ activated P,C-chelate complexes

Angewandte Chemie - International Edition

Volumn 43, Issue 35, 2004, Pages 4595-4597

  Lipowsky, Gunter ^a   Miller, Nicole ^a   Helmchen, Günter ^a  

^a UNIVERSITY OF HEIDELBERG   (Germany)

Author keywords

Alkylation; Allylic substitution; Asymmetric catalysis; Iridium; Phosphorus amidites

Indexed keywords

CATALYST SELECTIVITY; CATALYSTS; COPPER; IRIDIUM; STEREOCHEMISTRY;

ALLYLIC ALKYLATION; ENANTIOSELECTIVITY; LINEAR PRECURSORS;

ALKYLATION;

CARBON; CARBONIC ACID DERIVATIVE; CHELATE; IRIDIUM; PHOSPHORUS;

ALKYLATION; ARTICLE; CATALYSIS; ENANTIOSELECTIVITY; STRUCTURE ANALYSIS; SUBSTITUTION REACTION; X RAY CRYSTALLOGRAPHY;

EID: 5344223443     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200460016     Document Type: Article

References (27)

1. a) B. M. Trost, C. Lee in Catalytic Asymmetric Synthesis, 2nd Ed. (Ed.: I. Ojima), Wiley, New York, 2000, p. 593-649;
2. b) A. Pfaltz, M. Lautens in Comprehensive Asymmetric Catalysis I-III (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto), Springer, Berlin, 1999, p. 833-884;
3. c) B. M. Trost, M. L. Crawley, Chem. Rev. 2003, 103, 2921-2943.
4. a) S.-L. You, X.-Z. Zhu, Y.-M. Luo, X.-L. Hou, L.-X. Dai, J. Am. Chem. Soc. 2001, 123, 7471-7472, and references therein;
5. b) Vinyl epoxides: B. M. Trost, C. Jiang, Org. Lett. 2003, 5, 1563-1565, and references therein.
6. a) Ir: R. Takeuchi, Synlett 2002, 1954-1965;
7. b) First enantioselective reaction: J. P. Janssen, G. Helmchen, Tetrahedron Lett. 1997, 38, 8025-8026.
8. Mo: a) B. M. Trost, I. Hachiya, J. Am. Chem. Soc. 1998, 120, 1104-1105 (arylallyl derivatives);
9. b) B. M. Trost, S. Hildbrand, K. Dogra, J. Am. Chem. Soc. 1999, 121, 10416-10417 (alkenylallyl derivatives);
10. c) F. Glorius, A. Pfaltz, Org. Lett. 1999, 1, 141-144 (alkylallyl derivatives).
11. Ru: B. M. Trost, P. L. Fraisse, Z. T. Ball, Angew. Chem. 2002, 114, 1101-1103; Angew. Chem. Int. Ed. 2002, 41, 1059-1061.
12. Ru: B. M. Trost, P. L. Fraisse, Z. T. Ball, Angew. Chem. 2002, 114, 1101-1103; Angew. Chem. Int. Ed. 2002, 41, 1059-1061.
13. a) B. Bartels, G. Helmchen, Chem. Commun. 1999, 741-742;
14. b) B. Bartels, C. Garcia-Yebra, F. Rominger, G. Helmchen, Eur. J. Inorg. Chem. 2002, 2569-2586;
15. c) B. Bartels, C. Garcia-Yebra, G. Helmchen, Eur. J. Org. Chem. 2003, 1097-1103.
16. a) T. Ohmura, J. F. Hartwig, J. Am. Chem. Soc. 2002, 124, 15164-15165;
17. b) C. A. Kiener, C. Shu, C. Incarvito, J. F. Hartwig, J. Am. Chem. Soc. 2003, 125, 14272-14273;
18. c) G. Lipowsky, G. Helmchen, Chem. Commun. 2004, 116-117;
19. d) C. Welter, O. Koch, G. Lipowsky, G. Helmchen, Chem. Commun. 2004, 895-896.
20. a) F. Lopez, T. Ohmura, J. F. Hartwig, J. Am. Chem. Soc. 2003, 125, 3426-3427;
21. b) Kinetic resolution: C. Fischer, C. Defieber, T. Suzuki, E. M. Carreira, J. Am. Chem. Soc. 2004, 126, 1628-1629.
22. Additionally it has to be noted that the price of iridium is far below that of palladium. The prices per ounce (world market prices, October 2003) are: rhodium $500, palladium $199, iridium $90.
23. B. L. Feringa, Acc. Chem. Res. 2000, 33, 346-353.
24. B. Bartels, unpublished results.
25. The reason for this demand is the selective coordination of phosphorus in competition with the typically hard nucleophile.
26. Realization of the obvious possibility of generating the catalyst in the presence of the allylic substrate or another olefin in order to saturate the free coordination site was not successful.
27. Note added in proof: Use of a recently reported dimethoxy derivative of ligand L1 (compound 3b in K. Tissot-Croset, D. Polet, A. Alexakis, Angew. Chem. 2004, 43, 2426-2428) gave the following improved results for the reaction of 4a according to Table 2, entry 1: reaction time 45 min, yield 80%, regioselectivity 99:1, 98.5% ee; the regioselectivity of the reaction according to entry 5 was improved to 5e/6e = 88:12.