Remarkable rate acceleration of Pd(0)-catalyzed hydrogermylation of alkynes and dienes in water

Organic Letters

Volumn 3, Issue 16, 2001, Pages 2521-2524

  Kinoshita, Hidenori ^a   Nakamura, Tomoaki ^a   Kakiya, Hirotada ^a   Shinokubo, Hiroshi ^a   Matsubara, Seijiro ^a   Oshima, Koichiro ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; ALKYNE; PALLADIUM; WATER;

ARTICLE; CATALYSIS; CHEMISTRY; KINETICS; OXIDATION REDUCTION REACTION; STEREOISOMERISM;

ALKENES; ALKYNES; CATALYSIS; KINETICS; OXIDATION-REDUCTION; PALLADIUM; STEREOISOMERISM; WATER;

EID: 0035833724     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0161817     Document Type: Article

References (22)

1. (a) Li, C.-J.; Chan, T.-H. Organic Reactions in Aqueous Media; John Wiley: New York, 1997.
2. (b) Organic Synthesis in Water; Grieco, P. A., Ed.; Blackie Academic & Professional: London, 1998.
3. (c) Lubineau, A.; Augé, J. In Modern Solvent in Organic Synthesis; Knochel, P., Ed.; Springer-Verlag: Berlin, 1999; p 1.
4. For transition-metal-catalyzed reactions in aqueous media, see: (a) Sinou, D. In Modern Solvent in Organic Synthesis; Knochel, P., Ed.; Springer-Verlag: Berlin, 1999; p 41.
5. (b) Cornils, B.; Herrmann, W. A. Aqueous-Phase Organometallic Chemistry; Wiley-VCH: Weinheim, 1998.
6. (a) Corriu, R. J. P.; Moreau, J. J. E. J. Organomet. Chem. 1972, 40, 73.
7. (b) Dirnens, V.; Barabanov, D. I.; Liepins, E.; Ignatovich, L. M.; Lukevics, E. J. Organomet. Chem. 1992, 435, 257.
8. (c) Wada, F.; Abe, S.; Yonemura, N.; Kikukawa, K.; Matsuda, T. Bull. Chem. Soc. Jpn. 1991, 64, 1701.
9. (d) Piers, E.; Lemieux, R. J. Chem. Soc., Perkin Trans. 1 1995, 3.
10. (e) Widenhoefer, R. A.; Vadehra, A.; Cheruvu, P. K. Organometallics 1999, 18, 4614.
11. (f) Ichinose, Y.; Oda, H.; Oshima, K.; Utimoto, K. Bull. Chem. Soc. Jpn. 1987, 60, 3468. For a review of hydrogermylation, see; Wolfsberger, W. J. Prakt. Chem. 1992, 334, 453.
12. (f) Ichinose, Y.; Oda, H.; Oshima, K.; Utimoto, K. Bull. Chem. Soc. Jpn. 1987, 60, 3468. For a review of hydrogermylation, see; Wolfsberger, W. J. Prakt. Chem. 1992, 334, 453.
13. Hydrosilylation of alkynes to provide 1-silyl-1,3-dienes has been reported: (a) Kawanami, Y.; Yamamoto, K. Synlelt 1995, 1232.
14. (b) Lappert, M. F.; Nile, T. A.; Takahashi, S. J. Organomet. Chem. 1974, 72, 425.
15. (a) Nakamura, T.; Yorimitsu, H.; Shinokubo, H.; Oshima, K. Synlett 1999, 1415.
16. (b) Tanaka, S.; Nakamura, T.; Yorimitsu, H.; Shinokubo, H.; Oshima, K. Org. Lett. 2000, 2, 1911.
17. This reaction can be conducted in a separatory funnel. See Supporting Information.
18. Kobayashi, S.; Lam, W. W.-L.; Manabe, K. Tetrahedron Lett. 2000, 41, 6115 and references therein.
19. 4 and concentrated. Purification of the residual oil afforded a mixture of 1b and 2b (94/6 isomeric mixture. 0.49 g, 0.99 mmol) in 99% combined yield.
20. 2 provided 1f in 81% yield along with the regioisomer 2f in 11% yield.
21. Germylpalladation of 1,6-enynes has been reported to induce cyclization: see: Chatani, N.; Morimoto, T.; Muto, T.; Murai, S. J. Organomet. Chem. 1994, 473, 335.
22. For recent examples of palladium-catalyzed reactions in a hetero-geneous aqueous system, see: Uozumi, Y.; Shibatomi, K. J. Am. Chem. Soc. 2001, 123, 2919 and references therein.