Heteroatom-Directed, Palladium-Catalyzed, Regioselective Allylation: Substitution with Inversion

Journal of Organic Chemistry

Volumn 63, Issue 6, 1998, Pages 1748-1749

  Krafft, M E ^a   Wilson, A M ^a   Fu, Z ^a   Procter, M J ^a   Dasse, O A ^a  

^a FLORIDA STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001507379     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9802372     Document Type: Article

References (19)

1. For leading references, see: Tsuji, J. Tetrahedron 1986, 42, 4361. Frost, C. G.; Howarth, J.; Williams, J. M. J. Tetrahedron: Asymmetry 1992, 3, 1089.
2. For leading references, see: Tsuji, J. Tetrahedron 1986, 42, 4361. Frost, C. G.; Howarth, J.; Williams, J. M. J. Tetrahedron: Asymmetry 1992, 3, 1089.
3. Godleski, S. A. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon: Oxford, 1991; Vol. 4, p 585.
4. For a review on asymmetric allylations, see: Trost, B. M.; Van Vranken, D. L. Chem. Rev. 1996, 96, 395.
5. Keinan, E.; Sahai, M. J. Chem. Soc., Chem. Commun. 1984, 648.
6. Moreno-Manas, M.; Ribas, J. Tetrahedron Lett. 1989, 30, 3109.
7. Trost, B. M.; Weber, L.; Strege, P. E.; Fullerton, T. J.; Dietsche, T. J. Am. Chem. Soc. 1978, 100, 3416.
8. Genet, J. P.; Balabane, M.; Backvall, J. E.; Nystrom, J. E. Tetrahedron Lett. 1983, 24, 2745.
9. For example, see: Tsuji, J.; Kataoka, H.; Kobayashi, Y. Tetrahedron Lett. 1981, 22, 2575.
10. For an early explanation of the now generally accepted polarizing effect from an oxygenated functional group on the regiochemical outcome of the allylation, see: Genet, J. P.; Balabane, M.; Legras, Y. Tetrahedron Lett. 1982, 23, 331. Coordination of an allylic alcohol to palladium was proposed to be responsible for a regioselective alkylation at the terminus of the allyl moiety distal to the alcohol.
11. Sjogren, M. P. T.; Hansson, S.; Akermark, B. Organometallics 1994, 13, 1963. Akermark, B.; Zetterberg, K.; Hansson, S.; Krakenberger, B. J. Organomet. Chem. 1987, 335, 133.
12. Sjogren, M. P. T.; Hansson, S.; Akermark, B. Organometallics 1994, 13, 1963. Akermark, B.; Zetterberg, K.; Hansson, S.; Krakenberger, B. J. Organomet. Chem. 1987, 335, 133.
13. Leutenneger, U.; Umbricht, G.; Fahrni, C.; V. Matt, P.; Pfaltz, A. Tetrahedron 1992, 48, 2143. Pfaltz, A. Acc. Chem. Res. 1993, 26, 339. von Matt, P.; Lloyd-Jones, G. C.; Minidis, A. B. E.; Pfaltz, A.; Macko, L.; Neuberger, M.; Zehnder, M.; Ruegger, H.; Pregosin, P. S. Helv. Chim. Acta. 1995, 78, 265.
14. Leutenneger, U.; Umbricht, G.; Fahrni, C.; V. Matt, P.; Pfaltz, A. Tetrahedron 1992, 48, 2143. Pfaltz, A. Acc. Chem. Res. 1993, 26, 339. von Matt, P.; Lloyd-Jones, G. C.; Minidis, A. B. E.; Pfaltz, A.; Macko, L.; Neuberger, M.; Zehnder, M.; Ruegger, H.; Pregosin, P. S. Helv. Chim. Acta. 1995, 78, 265.
15. Leutenneger, U.; Umbricht, G.; Fahrni, C.; V. Matt, P.; Pfaltz, A. Tetrahedron 1992, 48, 2143. Pfaltz, A. Acc. Chem. Res. 1993, 26, 339. von Matt, P.; Lloyd-Jones, G. C.; Minidis, A. B. E.; Pfaltz, A.; Macko, L.; Neuberger, M.; Zehnder, M.; Ruegger, H.; Pregosin, P. S. Helv. Chim. Acta. 1995, 78, 265.
16. Typical Experimental Procedures. Preparation of 3a/4a. A solution of sulfide 1a (75 mg, 0.43 mmol) in THF (2.7 mL), catalyst 5 (9.6 mg, 5 mol %) and lithio diethyl malonate (1.5 mL, 0.43 mmol of a 0.3 M solution in THF) was heated at 75°C for 5 h. After cooling, the reaction mixture was filtered through a plug of silica gel and the solvent removed in vacuo. The residue was purified by flash column chromatography on silica gel eluting with 2% ethyl acetate/hexane to give a mixture of 3a and 4a as a colorless oil (103 mg, 0.38 mmol, 87%). Preparation of a 0.3 M Solution of Lithio Diethyl Malonate in THF. To a solution of diethyl malonate (320 mg, 2.0 mmol) in THF (6.7 mL) at -78°C was added n-BuLi (1.25 mL, 2.0 mmol of a 1.6 M solution in hexanes) dropwise over 10 min. The reaction mixture was stirred for 30 min at -78°C before being warmed to 0°C over 1 h.
17. Homoallylic secondary amines have been shown to react with allylic acetates under palladium catalysis to yield tertiary amines. Trost, B. M.; Godleski, S. A.; Genet, J. P. J. Am. Chem. Soc. 1978, 100, 3930.
18. Tin ethers have been shown to direct an oxygen nucleophile to an α-alkoxy π-allyl palladium intermediate proximal to the ether. Trost, B. M.; Tenaglia, A. Tetrahedron Lett. 1988, 29, 2931.
19. 1H NOE experiments at 500 MHz.