α-Selective Ni-catalyzed hydroalumination of aryl- and alkyl-substituted terminal alkynes: Practical syntheses of internal vinyl aluminums, halides, or boronates

Journal of the American Chemical Society

Volumn 132, Issue 32, 2010, Pages 10961-10963

  Gao, Fang ^a   Hoveyda, Amir H ^a  

^a BOSTON COLLEGE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

DIISOBUTYLALUMINUM HYDRIDE; DIRECT TREATMENT; ELECTROPHILES; GRAM SCALE; HIGH EFFICIENCY; HIGH SELECTIVITY; HYDROALUMINATION; HYDROALUMINATION REACTIONS; HYDROMETALATION; METHOXY; TERMINAL ALKYNE; VINYL HALIDES;

ACETYLENE; BORON; BORON COMPOUNDS; BYPRODUCTS; CHLORINE COMPOUNDS; ISOMERS; METAL COMPLEXES;

CATALYST SELECTIVITY;

ALKYL GROUP; ALKYNE DERIVATIVE; ALUMINUM DERIVATIVE; BORONIC ACID DERIVATIVE; ELECTROPHILE; HALIDE; METAL COMPLEX; NICKEL; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE; VINYL DERIVATIVE;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL REACTION; COMPLEX FORMATION; ISOMER; REACTION ANALYSIS; RELIABILITY; SYNTHESIS;

ALKYNES; ALUMINUM; BORONIC ACIDS; CATALYSIS; HALOGENS; NICKEL; STEREOISOMERISM; SUBSTRATE SPECIFICITY; VINYL COMPOUNDS;

EID: 77955564531     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja104896b     Document Type: Article

References (63)

1. For acyclic α-vinyl halide synthesis, see
2. Bromoboration/protodeboration of alkyl-substituted alkynes
3. Hara, S., Dojo, H., Takinami, S., and Suzuki, A. Tetrahedron Lett. 1983, 24, 731
4. Cr-mediated conversion of aldehydes to iodides
5. Takai, K., Nitta, K., and Utimoto, K. J. Am. Chem. Soc. 1986, 108, 7408
6. Terminal alkynes to iodides by hydroiodation (HI formed in situ from TMSI)
7. Kamiya, N., Chikami, Y., and Ishii, Y. Synlett 1990, 675
8. Ketones and aldehydes to iodides with phosphitohalides
9. Spaggiari, A., Vaccari, D., Davoli, P., Torre, G., and Prati, F. J. Org. Chem. 2007, 72, 2216
10. Terminal alkynes (no branched alkyl-substituted cases) to iodides by HI addition (generated from iodine/hydrophosphine)
11. Kawaguchi, S-i. and Ogawa, A. Org. Lett. 2010, 12, 1893
12. For synthesis of various cyclic and acyclic vinylboronates through Pd-catalyzed cross-coupling reactions involving the corresponding vinyl bromides and triflates, see
13. Takagi, J., Takahashi, K., Ishiyama, T., and Miyaura, N. J. Am. Chem. Soc. 2002, 124, 8001
14. For α-selective Ru-catalyzed hydrosilylation of alkynes, see
15. Trost, B. M. and Ball, Z. T. J. Am. Chem. Soc. 2005, 127, 17644
16. For a review on hydroaluminations of alkynes and alkenes, see
17. Eisch, J. J. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., and Schreiber, S. L., Eds.; Pergamon, Oxford, 1991; Vol. 8, pp 733.
18. For representative transformations where vinyl iodides are used in complex molecule synthesis, see
19. Liu, X., Henderson, J. A., Sasaki, T., and Kishi, Y. J. Am. Chem. Soc. 2009, 131, 16678 and references cited therein
20. For applications of vinylboronates in C-C bond formation, see
21. Miyaura, N. and Suzuki, A. Chem. Rev. 1995, 95, 2457
22. Kotha, S., Lahiri, K., and Kashinath, D. Tetrahedron 2002, 58, 9633
23. For example, see
24. Baba, S. and Negishi, E-i. J. Am. Chem. Soc. 1976, 98, 6729
25. Negishi, E-i., Okukado, N., King, A. O., Van Horn, D. E., and Spiegel, B. I. J. Am. Chem. Soc. 1978, 100, 2254
26. Lipshutz, B. H., Bülow, G., Lowe, R. F., and Stevens, K. L. Tetrahedron 1996, 52, 7265
27. Langille, N. F. and Jamison, T. F. Org. Lett. 2006, 8, 3761
28. Allylic alkylations
29. Lee, Y., Akiyama, K., Gillingham, D. G., Brown, M. K., and Hoveyda, A. H. J. Am. Chem. Soc. 2008, 130, 446
30. Akiyama, K., Gao, F., and Hoveyda, A. H. Angew. Chem., Int. Ed. 2010, 49, 419 Carbonyl additions: Biradar, D. B. and Gau, H.-M. Org. Lett. 2009, 11, 499
31. Vinylmetals (including vinylaluminums) can be accessed through carbo metallation of alkynes. For example, see
32. Wipf, P. and Lim, S. Angew. Chem., Int. Ed. Engl. 1993, 32, 1068
33. Fallis, A. G. and Forgione, P. Tetrahedron 2001, 57, 5899
34. Lipshutz, B. H., Butler, T., Lower, A., and Servesko, J. Org. Lett. 2007, 9, 3737
35. Zweifel, G. and Whitney, C. C. J. Am. Chem. Soc. 1967, 89, 2753
36. For use of alkyl-substituted vinylaluminums in Cu-catalyzed allylic alkylations, see
37. Reference 8a.
38. Zweifel, G., Snow, J. T., and Whitney, C. C. J. Am. Chem. Soc. 1968, 90, 7139
39. Uhl, W., Er, E., Hepp, A., Kösters, J., and Grunenberg, J. Organometallics 2008, 27, 3346
40. Uhl, W., Er, E., Hepp, A., Kösters, J., Layh, M., Rohling, M., Vinogradov, A., Würthwein, E.-U., and Ghavtadze, N. Eur. J. Inorg. Chem. 2009, 3307
41. Hydroalumination (dibal-H) of Si-substituted aryl alkynes, which proceeds efficiently and site selectively, has been introduced to address this shortcoming. The C-Si bond is removed by protodesilylation. See ref 8b.
42. For selectivity reversal in Ni-catalyzed H-P and H-S addition to terminal alkynes, see
43. Han, L.-B., Zhang, C., Yazawa, H., and Shimada, S. J. Am. Chem. Soc. 2004, 126, 5080
44. Eisch, J. J. and Foxton, M. W. J. Organomet. Chem. 1968, 12, P33
45. There is <2% reaction when phenylacetylene is treated with dibal-H in thf (at 22 °C, in 2 h).
46. 2) are complete in 2 h at 22 °C. For data regarding this class of catalytic hydroaluminations, see the Supporting Information.
47. Reference 1a
48. Moran, W. J. and Morken, J. P. Org. Lett. 2006, 8, 2413
49. For example, see
50. Morrill, C., Funk, T. W., and Grubbs, R. H. Tetrahedron Lett. 2004, 45, 7733
51. 2.
52. Synthesis of α-vinylboronates by an NHC-Cu-catalyzed hydroboration of a propargyl ether and a propargyl amide was recently reported to proceed with ∼90% α selectivity
53. Lee, Y., Jang, H., and Hoveyda, A. H. J. Am. Chem. Soc. 2009, 131, 18234
54. Tucker, C. E., Davidson, J., and Knochel, P. J. Org. Chem. 1992, 57, 3482
55. Pereira, S. and Srebnik, M. Tetrahedron Lett. 1996, 37, 3283
56. Ohmura, T., Yamamoto, Y., and Miyaura, N. J. Am. Chem. Soc. 2000, 122, 4990
57. Wang, Y. D., Kimball, G., Prashad, A. S., and Wang, Y. Tetrahedron Lett. 2005, 46, 8777
58. For a Cu-catalyzed hydroboration of phenylacetylene that affords the terminal vinylboronate, see
59. Lee, J.-E., Kwon, J., and Yun, J. Chem. Commun. 2008, 733. This procedure is ineffective with alkyl-substituted alkynes
60. Takahashi, K., Ishiyama, T., and Miyaura, N. J. Organomet. Chem. 2001, 625, 47
61. 2Al-Ni-H]; addition of Ni-H across the alkyne and subsequent alkenyl-Al reductive elimination regenerates the Ni(0) complex. See
62. Eisch, J. J., Sexsmith, S. R., and Fichter, K. C. J. Organomet. Chem. 1990, 382, 273
63. Eisch, J. J., Ma, X., Singh, M., and Wilke, G. J. Organomet. Chem. 1997, 527, 301