Carbocupration of 1-alkynylphosphines followed by trapping with electrophiles

Organic Letters

Volumn 9, Issue 10, 2007, Pages 2031-2033

  Kanemura, Shigenari ^a   Kondoh, Azusa ^a   Yorimitsu, Hideki ^a   Oshima, Koichiro ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 34249332008     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0706657     Document Type: Article

References (25)

1. Baya, M.; Buil, M. L.; Esteruelas, M. A.; Oñate, E. Organometallics 2005, 24, 2030-2038 and references cited therein.
2. (a) Organophosphorus Reagents; Murphy, P. J., Ed.; Oxford University Press: Oxford, UK, 2004.
3. (b) Ohmiya, H.; Yorimitsu, H.; Oshima, K. Angew. Chem., Int. Ed. 2005, 44, 2368-2370 and references cited therein.
4. (a) Normant, J. F.; Alexakis, A. Synthesis 1981, 841-870.
5. (b) Lipshutz, L. H.; Sengupta, S. Org. React. 1992, 41, 135-631.
6. Cross-coupling reaction of alkenyl inflates with secondary phosphines provides an alternative route, (a) Gilbertson, S. R.; Fu, Z.; Starkey, G. W. Tetrahedron Lett. 1999, 40, 8509-8512.
7. (b) Kazankova, M. A.; Trostyanskaya, I. G.; Lutsenko, S. V.; Beletskaya, I. P. Tetrahedron Lett. 1999, 40, 569-572.
8. (a) Meijer, J.; Westmijze, H.; Vermeer, P. Recl. Trav. Chim. Pays-Bas 1976, 95, 102-104.
9. (b) Alexakis, A.; Cahiez, G.; Normant, J. F.; Villieras, J. Bull. Soc. Chim. Fr. 1977, 693-698.
10. (a) Kondoh, A.; Yorimitsu, H.; Oshima, K. J. Am. Chem. Soc. 2007, 129, 4099-4104.
11. (b) Kondoh, A.; Yorimitsu, H.; Oshima, K. Org. Lett. 2007, 9, 1383-1385.
12. Lipshutz, B. H. In Organometallics in Synthesis, A Manual, 2nd ed.; Schlosser, M., Ed.; John Wiley & Sons: Chichester, UK, 2002, Chapter VI/3.2.3.
13. Without adding sulfur, the results obtained in this paper were not reproducible. The lack of reproducibility originated mainly from formation of the corresponding phosphine oxide during tedious workup and the difficulty in decomplexation of copper - phosphine complexes generated in situ.
14. 2 (0.15 g, 0.75 mmol) was placed in a 30-mL reaction flask under argon. Ether (3.0 mL) was added and the mixture was cooled to -78 °C. BuMgBr (1.0 M ether solution, 1.6 mL, 1.6 mmol) was then added. After the mixture was stirred for l h at -78 °C, 1a (0.14 g, 0.50 mmol) was added. The mixture was stirred at 25 °C for 2.5 h. Allyl bromide (0.21 g, 1.8 mmol) was then added. After 1 h, crystalline sulfur (24 mg, 0.75 mmol) was added. The whole mixture was stirred for 30 min, and the reaction was quenched with saturated ammonium chloride solution (10 mL). Extractive workup followed by purification on silica gel provided 3a (0.17 g, 0.40 mmol, 80%) as a white solid.
15. Attempts to allylate the corresponding dimetallic species resulted in failure, obtaining mixtures of the non-, mono-, and diallylated compounds.
16. Without TMEDA, 5a was obtained in 31% yield, along with the protonated product in 37% yield. The exact role of TMEDA is not clear.
17. 2, provided a mixture containing triphenylphosphine sulfide, phenylacetylene, and 65% yield of the sulfide of 1a. In general, magnesium cuprates afforded less complex mixtures in the present reaction than lithium cuprates.
18. Attempts to trap the corresponding alkenylcopper intermediate with allyl bromide resulted in failure.
19. Lipshutz, B. H.; Hackmann, C. J. Org. Chem. 1994, 59, 7437-7444.
20. (a) Cantat, T.; Ricard, L.; Mézailles, N.; Le Floch, P. Organometallics 2006, 25, 6030-6038.
21. (b) Bookham, J. L.; Conti, D.; McFarlane, H. C. E.; McFarlane, W.; Thornton-Pett, M. J. Chem. Soc., Dalton Trans. 1994, 1791-1797.
22. (c) Goli, M. B.; Grim, S. O. Tetrahedron Lett. 1991, 32, 3631-3634.
23. Experimental procedure: The alkenylcopper intermediate was prepared by the same procedure described in ref 8. DPPE ( 1.0 g, 2.5 mmol) and chlorodiphenylphosphine (0.39 g, 1.8 mmol) were added to the reaction mixture at 25 °C. After the mixture was stirred for 2 h, crystalline sulfur (0.33 g, 10.3 mmol) was added. The whole mixture was stirred for 1 h, and the reaction was quenched with saturated ammonium chloride solution (10 mL). Extraction followed by concentration gave a solid. Purification by gel permeation chromatography provided 7a (0.25 g, 0.43 mmol, 85%) as a white solid.
24. Matano, Y.; Miyajima, T.; Nakabuchi, T.; Imahori, H.; Ochi, N.; Sakaki, S. J. Am. Chem. Soc. 2006, 128, 11760-11761.
25. Experimental procedure: A mixture of 7a (0.059 g, 0.10 mmol) and tris(dimethylamino)phosphine (0.098 g, 0.60 mmol) in toluene (2.0 mL) was heated at reflux for 13 h under argon. The mixture was then allowed to cool to room temperature. Water (10 mL) was added, and the product was extracted with a mixture of hexane and ethyl acetate (3 × 10 mL). The combined organic layer was dried over sodium sulfate and concentrated in vacuo. Chromatographic purification on silica gel yielded 10 (0.041 g, 0.077 mmol, 77%) as a white solid.