Catalytic enantioselective alkynylation of trifluoromethyl ketones: Pronounced metal fluoride effects and implications of zinc-to-titanium transmetallation

Angewandte Chemie - International Edition

Volumn 50, Issue 15, 2011, Pages 3538-3542

  Zhang, Guang Wu ^a   Meng, Wei ^a   Ma, Hai ^a   Nie, Jing ^a   Zhang, Wen Qin ^a   Ma, Jun An ^a,b  

^a TIANJIN UNIVERSITY   (China)

^b NANKAI UNIVERSITY   (China)

Author keywords

alkynylation; asymmetric catalysis; enantioselectivity; fluorides; titanium

Indexed keywords

ALKYNYLATIONS; AS-LIGANDS; ASYMMETRIC CATALYSIS; CINCHONA ALKALOID; ENANTIOSELECTIVE; FLUORIDES; HIGH YIELD; METAL FLUORIDE; TERTIARY ALCOHOLS; TRANSMETALATION; TRANSMETALLATION; TRIFLUOROMETHYLKETONE;

CATALYSIS; CHELATION; FLUORINE COMPOUNDS; KETONES; SYNTHESIS (CHEMICAL); TITANIUM;

ENANTIOSELECTIVITY;

FLUORIDE; FLUORINE; KETONE; TITANIUM; ZINC;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY; ELECTROSPRAY MASS SPECTROMETRY; STEREOISOMERISM;

CATALYSIS; FLUORIDES; FLUORINE; KETONES; MOLECULAR STRUCTURE; SPECTROMETRY, MASS, ELECTROSPRAY IONIZATION; STEREOISOMERISM; TITANIUM; ZINC;

EID: 79953244889     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201007341     Document Type: Article

References (53)

1. For selected reviews, see: a) Modern Acetylene Chemistry (Eds.:, P. J. Stang, F. Diederich,), VCH, Weinheim, 1995
2. N. Ljungdahl, N. Kann, Angew. Chem. 2009, 121, 652-654
3. Angew. Chem. Int. Ed. 2009, 48, 642-644
4. D. A. Engel, G. B. Dudley, Org. Biomol. Chem. 2009, 7, 4149-4158.
5. For recent reviews, see: a) L. Pu, Tetrahedron 2003, 59, 9873-9886
6. P. G. Cozzi, R. Hilgraf, N. Zimmermann, Eur. J. Org. Chem. 2004, 4095-4105
7. D. J. Ramón, M. Yus, Angew. Chem. 2004, 116, 286-289
8. Angew. Chem. Int. Ed. 2004, 43, 284-287
9. J. M. Betancort, C. García, P. J. Walsh, Synlett 2004, 749-760
10. G. Lu, Y.-M. Li, X.-S. Li, A. S. C. Chan, Coord. Chem. Rev. 2005, 249, 1736-1744
11. B. M. Trost, A. H. Weiss, Adv. Synth. Catal. 2009, 351, 963-983
12. L. Lin, R. Wang, Curr. Org. Chem. 2009, 13, 1565-1576.
13. For recent examples of titanium complexes as catalysts in asymmetric alkynylation, see: a) G. Gao, R.-G. Xie, L. Pu, Proc. Natl. Acad. Sci. USA 2004, 101, 5417-5420
14. D. Moore, L. Pu, Org. Lett. 2002, 4, 1855-1857
15. G. Gao, D. Moore, R.-G. Xie, L. Pu, Org. Lett. 2002, 4, 4143-4146
16. G. Lu, X. Li, W. L. Chan, A. S. C. Chan, Chem. Commun. 2002, 172-173
17. X.-S. Li, G. Lu, W. H. Kwok, A. S. C. Chan, J. Am. Chem. Soc. 2002, 124, 12366-12367
18. L. Lin, X. Jiang, W. Liu, L. Qiu, Z. Xu, J. Xu, A. S. C. Chan, R. Wang, Org. Lett. 2007, 9, 2329-2332.
19. For recent reviews, see: a) P. Kirsch, Modern Fluoroorganic Chemistry, Wiley-VCH, Weinheim, 2004
20. Special Issue on "Fluorine in the Life Sciences", ChemBioChem 2004, 5, 557-726
21. R. D. Chambers, Fluorine in Organic Chemistry, Blackwell, Oxford, UK, 2004
22. K. Müller, C. Faeh, F. Diederich, Science 2007, 317, 1881-1886
23. J.-A. Ma, D. Cahard, Chem. Rev. 2008, 108, PR 1-43
24. K. L. Kirk, Org. Process Res. Dev. 2008, 12, 305-321
25. J. Nie, H.-C. Guo, D. Cahard, J.-A. Ma, Chem. Rev. 2011, 111, 455-529.
26. A. S. Thompson, E. G. Corley, M. F. Huntington, E. J. J. Grabowski, Tetrahedron Lett. 1995, 36, 8937-8940
27. A. Thompson, E. G. Corley, M. F. Huntington, E. J. J. Grabowski, J. F. Remenar, D. B. Collum, J. Am. Chem. Soc. 1998, 120, 2028-2038
28. L. Tan, C. Chen, R. D. Tillyer, E. J. J. Grabowski, P. J. Reider, Angew. Chem. 1999, 111, 724-727
29. Angew. Chem. Int. Ed. 1999, 38, 711-713
30. F. Xu, R. A. Reamer, R. Tillyer, J. M. Cummins, E. J. J. Grabowski, P. J. Reider, D. B. Collum, J. C. Huffman, J. Am. Chem. Soc. 2000, 122, 11212-11218
31. B. Jiang, Y. Feng, Tetrahedron Lett. 2002, 43, 2975-2977.
32. We are aware of one catalytic but only moderately enantioselective alkynylation of trifluoromethyl ketones using copper complexes. In this case, a very limited range of substrates were tested and only moderate enantioselectivity was observed, see:, R. Motoki, M. Kanai, M. Shibasaki, Org. Lett. 2007, 9, 2997-3000.
33. For biocatalytic kinetic resolution of racemic substrates for the preparation of chiral trifluoromethylated propargylic tertiary alcohols, see: a) B. Heinze, R. Kourist, L. Fransson, K. Hult, U. T. Bornscheuer, Protein Eng. Des. Sel. 2007, 20, 125-131
34. S. Bartsch, R. Kourist, U. T. Bornscheuer, Angew. Chem. 2008, 120, 1531-1534
35. Angew. Chem. Int. Ed. 2008, 47, 1508-1511.
36. Hydride and fluoride are classified as hard ligands in coordination chemistry. In addition, the Van der Waals radius of fluorine of 1.35 Å renders this element only slightly larger (12.5%) than hydrogen (1.20 Å).
37. For selected reviews, see: a) B. L. Pagenkopf, E. M. Carreira, Chem. Eur. J. 1999, 5, 3437-3442
38. K. Fagnou, M. Lautens, Angew. Chem. 2002, 114, 26-49
39. Angew. Chem. Int. Ed. 2002, 41, 26-47; for selected examples, see
40. D. R. Gauthier, E. M. Carreira, Angew. Chem. 1996, 108, 2521-2523
41. Angew. Chem. Int. Ed. Engl. 1996, 35, 2363-2365
42. X. Verdaguer, U. E. W. Lange, M. T. Reding, S. L. Buchwald, J. Am. Chem. Soc. 1996, 118, 6784-6785
43. J. Krüger, E. M. Carreira, J. Am. Chem. Soc. 1998, 120, 837-838
44. R. Dorta, P. Egli, F. Zürcher, A. Togni, J. Am. Chem. Soc. 1997, 119, 10857-10858
45. B. L. Pagenkopf, E. M. Carreira, Tetrahedron Lett. 1998, 39, 9593-9596.
46. The enantioselective alkynylation of 2'-chloro-2,2,2-trifluoroaceto- phenone with phenylacetylene; adduct 85% yield, 40% ee. (by using QN).
47. The B3LYP calculations were carried out according to Ahlrichs's SVP all electron basis set model using pseudo-potential basis sets (LAN2MB) for Ba, Zn, Ti, and 6-31G(d) basis set for C, H, O, N, F. Computational details and references are given in the Supporting Information.
48. For several examples of a titanium(IV)/complex that contains the alkoxides and one tertiary amine donor, see: a) K.-H. Wu, H.-M. Gau, Organometallics 2004, 23, 580-588
49. L. Lavanant, L. Toupet, C. W. Lehmann, J.-F. Carpentier, Organometallics 2005, 24, 5620-5633
50. S.-H. Hsieh, H.-M. Gau, Chirality 2006, 18, 569-1574
51. J. K. Day, R. E. Baghurst, R. R. Strevens, M. E. Light, M. B. Hursthouse, B. F. Stengel, I. A. Fallis, S. Aldridge, New J. Chem. 2007, 31, 135-143.
52. During the revision of this manuscript, a palladium-catalyzed enantioselective alkynylation of trifluoropyruvate was described:, K. Aikawa, Y. Hioki, K. Mikami, Org. Lett. 2010, 12, 5716-5719.
53. The enantioselective alkynylation of benzaldehyde with the complex I under unoptimized reaction conditions gave the adduct in quantitative yield with 70% ee. We thank one of the reviewers for suggesting that we examine the reactivity of complex I towards the aldehyde substrate.