Isomerization of alkynes to 1,3-dienes under rhodium or palladium catalysis

Synlett

Volumn , Issue 11, 2006, Pages 1783-1785

  Yasui, Hiroto ^a   Yorimitsu, Hideki ^a   Oshima, Koichiro ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

1,3 dienes; Alkynes; Isomerization; Palladium; Rhodium

Indexed keywords

1,3 DIENE DERIVATIVE; ALKADIENE; ALKYNE DERIVATIVE; PALLADIUM; RHODIUM; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; ISOMERIZATION;

EID: 33746307284     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2006-947325     Document Type: Article

References (11)

1. (a) Trost, B. M.; Schmidt, T. J. Am. Chem. Soc. 1988, 110, 2301.
2. (b) Ma, D.; Lin, Y.; Lu, X.; Yu, Y. Tetrahedron Lett. 1988, 29, 1045.
3. (c) Ma, D.; Yu, Y.; Lu, X. J. Org. Chem. 1989, 54, 1105.
4. (d) Ma, D.; Lu, X. Tetrahedron Lett. 1989, 30, 843.
5. Isomerization of propargyl ethers: (a) Hirai, K.; Suzuki, H.; Morooka, Y.; Ikawa, T. Tetrahedron Lett. 1980, 21, 3413.
6. (b) Isomerization of perfluoroalkylalkynes: Wang, Z.; Lu, X. Tetrahedron 1995, 51, 11765.
7. (c) Isomerization as a side reaction: Kadota, I.; Shibuya, A.; Lutete, L. M.; Yamamoto, Y. J. Org. Chem. 1999, 64, 4570.
8. (d) Ruthenium-catalyzed isomerization: Shiotsuki, M.; Ura, Y.; Ito, T.; Wada, K.; Kondo, T.; Mitsudo, T. J. Organomet. Chem. 2005, 689, 3168.
9. 2 and allyltributylstannane in refluxing xylene.
10. 2 (4.9 mg, 0.01 mmol) was placed in a 20 mL reaction flask under argon. TMEDA (2.3 mg, 0.02 mmol, dissolved in 2 mL of xylene), alkyne 1b (93 mg, 0.50 mmol, dissolved in 2 mL of xylene), and allyltributylstannane (199 mg, 0.6 mmol, dissolved in 2 mL of xylene) were sequentially added at ambient temperature. After being stirred for 12 h at 140 °C, the reaction mixture was cooled to ambient temperature, and HCl (6 M, 5 mL) was added. After being stirred for additional 1 h, the product was extracted with hexane (2 × 10 mL). The combined organic phase was dried over Na2SO4. Evaporation followed by silica gel column purification afforded 1,3-diene 2b (78.2 mg, 0.42 mmol, 84%). The obtained 2b showed the identical spectra in the literature, see: Miyaura, N.; Yamada, K.; Suginome, H.; Suzuki, A. J. Am. Chem. Soc. 1985, 107, 972.
11. 6 (%): C, 59.63; H, 5.00; Found: C, 59.70; H, 4.94.