Dehydrogenative silylation of terminal alkynes catalyzed by Ytterbium- imine complexes

Journal of Organic Chemistry

Volumn 63, Issue 25, 1998, Pages 9265-9269

  Takaki, Ken ^a   Kurioka, Masanobu ^a   Kamata, Tohru ^a   Takehira, Katsuomi ^a   Makioka, Yoshikazu ^b   Fujiwara, Yuzo ^b  

^a HIROSHIMA UNIVERSITY   (Japan)

^b KYUSHU UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNE; IMINE; SILANE DERIVATIVE; YTTERBIUM;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CATALYSIS; COMPLEX FORMATION; OLIGOMERIZATION; PROTON NUCLEAR MAGNETIC RESONANCE; SYNTHESIS;

EID: 0032509368     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo981008i     Document Type: Article

References (39)

1. (a) Hiyama, T.; Kusumoto, T. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 8, pp 763-792.
2. (b) Ojima, I. In The Chemistry of Organic Silicon Compounds; Patai, S., Rappoport, Z., Eds.; Wiley: New York, 1989; pp1479-1526.
3. Liu, H. Q.; Harrod, J. F. Can. J. Chem. 1990, 68, 1100-1105.
4. (a) Itoh, M.; Mitsuzuka, M.; Utsumi, T.; Iwata, K.; Inoue, K. J. Organomet. Chem. 1994, 476, C30-C31.
5. (b) Itoh, M.; Mitsuzuka, M.; Iwata, K.; Inoue, K. Macromolecules 1994, 27, 7917-7919.
6. (a) Voronkov, M. G.; Pukhnarevich, V. B.; Ushakova, N. I.; Tsykhanskaya, I. I.; Albanov, A. I.; Vitkovskii, V. Yu. Zh. Obshch. Khim. 1985, 55, 94-100; Chem. Abstr. 1985, 103, 6399d.
7. (a) Voronkov, M. G.; Pukhnarevich, V. B.; Ushakova, N. I.; Tsykhanskaya, I. I.; Albanov, A. I.; Vitkovskii, V. Yu. Zh. Obshch. Khim. 1985, 55, 94-100; Chem. Abstr. 1985, 103, 6399d.
8. (b) Voronkov, M. G.; Ushakova, N. I.; Tsykhanskaya, I. I.; Pukhnarevich, V. B. J. Organomet. Chem. 1984, 264, 39-48.
9. (c) Voronkov, M. G.; Druzhdzh, P. V.; Pukhnarevich, V. B. Zh. Obshch. Khim. 1980, 50, 1662; Chem. Abstr. 1980, 93, 220825h.
10. (c) Voronkov, M. G.; Druzhdzh, P. V.; Pukhnarevich, V. B. Zh. Obshch. Khim. 1980, 50, 1662; Chem. Abstr. 1980, 93, 220825h.
11. 3: Fernandez, M. J.; Oro, L. A. J. Mol. Catal. 1988, 45, 7-15.
12. 6: Jun, C.-H.; Crabtree, R. H. J. Organomet. Chem. 1993, 447, 177-187.
13. 3: Fuchikami, T.; Shimizu, R. 70th Annual Meeting of the Chemical Society of Japan, Tokyo, March 1996; 2J230.
14. Itoh, M.; Kobayashi, M.; Ishikawa, J. Organometallics 1997, 16, 3068-3070.
15. (a) Sakakura, T.; Lautenschlager, H.-J.; Tanaka, M. J. Chem. Soc., Chem. Commun. 1991, 40-41.
16. (b) Molander, G. A.; Julius, M. J. Org. Chem. 1992, 57, 6347-6351.
17. (c) Molander, G. A.; Nichols, P. J. J. Am. Chem. Soc. 1995, 117, 4415-4416.
18. (d) Molander, G. A.; Retsch, W. H. Organometallics 1995, 14, 4570-4575.
19. (e) Fu, P.-F.; Brard, L.; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 7157-7168.
20. Forsyth, C. M.; Nolan, S. P.; Marks, T. J. Organometallics 1991, 10, 2543-2545.
21. Heeres, H. J.; Teuben, J. H. Organometallics 1991, 10, 1980-1986.
22. (a) Evans, W. J.; Keyer, R. A.; Ziller, J. W. Organometallics 1990, 9, 2628-2631.
23. (b) Heeres, H. J.; Nijhoff, J.; Teuben, J. H. Organometallics 1993, 12, 2609-2617.
24. (c) Evans, W. J.; Keyer, R. A.; Ziller, J. W. Organometallics 1993, 12, 2618-2633.
25. (d) Forsyth, C. M.; Nolan, S. P.; Stern, C. L.; Marks, T. J. Organometallics 1993, 12, 3618-3623.
26. Makioka, Y.; Taniguchi, Y.; Fujiwara, Y.; Takaki, K.; Hou, Z.; Wakatsuki, Y. Organometallics 1996, 15, 5476-5478.
27. Makioka, Y.; Saiki, A.; Takaki, K.; Taniguchi, Y.; Kitamura, T.; Fujiwara, Y. Chem. Lett. 1997, 27-28.
28. Although the number of the coordinated HMPA is unknown, equivalents of this additive used for generation of the complexes are tentatively shown as a coordination number. The silylation did not take place with the imine complex prepared in the absence of HMPA.
29. n = 1.1) was isolated in 29% yield by aqueous workup, followed by short column chromatography on silica gel using hexanes-ethyl acetate eluent (1/1).
30. The products 4a and 4b were obtained in 52% and 18% yields or 67% and 16% yields, respectively, when the ratio was 1/1 or 1/2.
31. For 1-alkynes with lanthanide carbyl complexes, see: (a) ref 10. (b) Thompson, M. E.; Baxter, S. M.; Bulls, A. R.; Burger, B. J.; Nolan, M. C.; Santarsiero, B. D.; Schaefer, W. P.; Bercaw, J. E. J. Am. Chem. Soc. 1987, 109, 203-219. For 1-alkyne with lanthanide hydride complexes, see: (c) ref 10a. (d) ref 10c. (e) Evans, W. J.; Meadows, J. H.; Hunter, W. E.; Atwood, J. L. J. Am. Chem. Soc. 1984, 106, 1291-1300.
32. For 1-alkynes with lanthanide carbyl complexes, see: (a) ref 10. (b) Thompson, M. E.; Baxter, S. M.; Bulls, A. R.; Burger, B. J.; Nolan, M. C.; Santarsiero, B. D.; Schaefer, W. P.; Bercaw, J. E. J. Am. Chem. Soc. 1987, 109, 203-219. For 1-alkyne with lanthanide hydride complexes, see: (c) ref 10a. (d) ref 10c. (e) Evans, W. J.; Meadows, J. H.; Hunter, W. E.; Atwood, J. L. J. Am. Chem. Soc. 1984, 106, 1291-1300.
33. For 1-alkynes with lanthanide carbyl complexes, see: (a) ref 10. (b) Thompson, M. E.; Baxter, S. M.; Bulls, A. R.; Burger, B. J.; Nolan, M. C.; Santarsiero, B. D.; Schaefer, W. P.; Bercaw, J. E. J. Am. Chem. Soc. 1987, 109, 203-219. For 1-alkyne with lanthanide hydride complexes, see: (c) ref 10a. (d) ref 10c. (e) Evans, W. J.; Meadows, J. H.; Hunter, W. E.; Atwood, J. L. J. Am. Chem. Soc. 1984, 106, 1291-1300.
34. For 1-alkynes with lanthanide carbyl complexes, see: (a) ref 10. (b) Thompson, M. E.; Baxter, S. M.; Bulls, A. R.; Burger, B. J.; Nolan, M. C.; Santarsiero, B. D.; Schaefer, W. P.; Bercaw, J. E. J. Am. Chem. Soc. 1987, 109, 203-219. For 1-alkyne with lanthanide hydride complexes, see: (c) ref 10a. (d) ref 10c. (e) Evans, W. J.; Meadows, J. H.; Hunter, W. E.; Atwood, J. L. J. Am. Chem. Soc. 1984, 106, 1291-1300.
35. For 1-alkynes with lanthanide carbyl complexes, see: (a) ref 10. (b) Thompson, M. E.; Baxter, S. M.; Bulls, A. R.; Burger, B. J.; Nolan, M. C.; Santarsiero, B. D.; Schaefer, W. P.; Bercaw, J. E. J. Am. Chem. Soc. 1987, 109, 203-219. For 1-alkyne with lanthanide hydride complexes, see: (c) ref 10a. (d) ref 10c. (e) Evans, W. J.; Meadows, J. H.; Hunter, W. E.; Atwood, J. L. J. Am. Chem. Soc. 1984, 106, 1291-1300.
36. Successive addition of 1-hexyne and cyclohexanone to 1a (1:1: 1) in THF gave 1-(1-hexynyl)cyclohexanol in 77% yield, which suggests the generation of alkynide species A from 1-hexyne and 1a.
37. 2, in THF at 100 °C has been observed; see ref 10c.
38. The active species is likely to be divalent, because the deep reddish-black solution, a typical color of these divalent species, remains unchanged when the reaction proceeds smoothly. In contrast, the reaction ceases when the color changes to brownish-yellow.
39. Treatment of p-tolualdehyde with 1a (1.0 equiv) in toluene gave the corresponding pinacol in 80% yield.