Simple construction of bicyclo[4.3.0]nonane, bicyclo[3.3.0]octane, and related benzo derivatives by palladium-catalyzed cycloalkenylation

Organic Letters

Volumn 4, Issue 24, 2002, Pages 4293-4296

  Toyota, Masahiro ^a   Ilangovan, Andivelu ^a   Okamoto, Rei ^a   Masaki, Tomohito ^a   Arakawa, Makoto ^a   Ihara, Masataka ^a  

^a TOHOKU UNIVERSITY   (Japan)

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EID: 0037771626     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol020187u     Document Type: Article

References (23)

1. Tsuji, J. Palladium Reagents and Catalysts; Wiley: New York, 1995.
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3. Toyota, M.; Wada, T.; Ihara, M. J. Org. Chem. 2000, 65, 4565-4570.
4. Toyota, M.; Odashima, T.; Ihara, M. J. Am. Chem. Soc. 2000, 122, 9036-9037.
5. (a) Pioneers: Ito, Y.; Aoyama, H.; Hirao, T.; Mochizuki, A.; Saegusa, T. J. Am. Chem. Soc. 1979, 101, 494-496.
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16. Representative Procedure: To a stirred solution of homoallylmag-nesium bromide13 (5.7 mmol) in anhydrous THF (7.8 mL) were added CuBr SMe2 (95 mg, 0.46 mmol) and HMPA (1.3 mL, 7.5 mmol) at -78 C. After 0.5 h of stirring at -78 C, an anhydorus THF solution (3.1 mL) of 2,3-dimethylcyclopentenone (0.30 mL, 3.0 mmol) and TMSCI (1.1 mL, 8.7 mmol) was added dropwise at -78 C. The mixture was stirred at -78 C tor 1 h and then Et3N (0.9 mL, 6.5 mmol) was added at -78 C in one portion. The reaction mixture was warmed to room temperature over 2 h and stirred overnight. After dilution with pentane, the organic layer was washed three times with water, saturated NaHCO3 solution and brine and dried over MgSO4. After removal of the solvent, the residue was chro-matographed on silica gel with hexane to provide silyl enol ether 3c (672 mg, 94%) as a colorless oil. 1H NMR (400 MHz) (C6D6) 5.80-5.77 (1H, m), 5.05 (1H, br d, J=16.0 Hz), 4.97 (1H, br d, J=12.0 Hz), 1.53 (3H, br s), 0.97 (3H, s), and 0.15 (9H, s).
17. Procedure for Palladium-Catalyzed Cycloalkenylation: To a stirred solution of silyl enol ether 3c (154 mg, 0.68 mmol) in DMSO (7.7 mL) was added palladium acetate (15.2 mg, 0.068 mmol) at room temperature. The mixture was stirred at 45 C for 20 h under 1 atm of oxygen. After being cooled to room temperature, the mixture was diluted with water. The resulting mixture was extracted three times with Et2O, and the combined ethereal layers were washed with brine, dried over MgSO4, and evaporated to yield an oil, which was chromatographed. Elution with haxanes-EtOAc (9:1) afforded exo-olefin 4c (46.4 mg, 41%), endo-olefin 5c (7.9 mg, 8%), and ketone 7c (0.55 mg, 1%). All the products were obtained as a colorless oil. 4c: IR (neat) 1738 cm-1. 1H NMR (400 MHz) (CDCl3) 4.96-4.95 (2H, br s), 1.02 (3H, s), and 1.01 (3H, S). 5c: IR (neat) 1738 cm-1. 1H NMR (400 MHz) (CDCl3) 5.33 (1H, br s), 1.55 (3H, br s), 1.08 (3H, s), and 0.98 (3H, s).
18. There is an interesting example of C-C bond formation between aromatic rings and multiple bonds utilizing strong acid and Pd(II). Jia, C.; Piao, D.; Oyamada, J.; Lu, W.; Kitamura, T.; Fujiwara, Y. Science, 2000 287, 1992-1995.
19. 16
20. Benson, R. E.; McKusick, B. C. Organic Synthses; Wiley: New York, 1963; Collect Vol. IV, pp 746-752.
21. Ratilainen, J.; Huhtala, P.; Karjalainen, A.; Haapalinna, A.; Virtanen, R.; Lehtimaki, J. U.S. Patent 6362211 B2, 2002.
22. Bruce, I.; Cooke, N. G.; Diorazio, L. J.; Hall, R. G.; Irving, E. Tetrahedron Lett. 1999, 40, 4279-4282.
23. Kakiuchi, K.; Fujioka, Y.; Yamamura, H.; Tsutsumi, K.; Morimoto, T.; Kurosawa, H. Tetrahedron Lett. 2001, 42, 7595-7598.