Surprisingly mild "enolate-counterion-free" Pd(0)-catalyzed intramolecular allylic alkylations

Organic Letters

Volumn 7, Issue 6, 2005, Pages 995-998

  Madec, David ^a   Prestat, Guillaume ^a   Martini, Elisabetta ^a   Fristrup, Peter ^b   Poli, Giovanni ^a   Norrby, Per Ola ^b  

^a SORBONNE UNIVERSITÉ   (France)

^b TECHNICAL UNIVERSITY OF DENMARK   (Denmark)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYL COMPOUND; PALLADIUM COMPLEX;

ALKYLATION; ARTICLE; CALCULATION; CATALYSIS; CHEMICAL REACTION; CYCLIZATION; MOLECULAR INTERACTION; PHASE TRANSITION; REACTION ANALYSIS; VALIDATION PROCESS;

EID: 18244393989     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol047548l     Document Type: Article

References (28)

1. (a) Giambastiani, G.; Pacini, B.; Porcelloni, M.; Poli, G. J. Org. Chem. 1998, 63, 804-807.
2. (b) Poli, G.; Giambastiani, G. J. Org. Chem. 2002, 67, 9456-9459.
3. (c) Thorimbert, S.; Giambastiani, G.; Commandeur, C.; Vitale, M.; Poli, G.; Malacria, M. Eur. J. Org. Chem. 2003, 2702-2708.
4. (d) Lemaire, S.; Giambastiani, G.; Prestat, G.; Poli, G. Eur. J. Org. Chem. 2004, 2840-2847.
5. BSA: N,O-Bis(trimethylsilyl)acetamide.
6. Lemaire, S.; Prestat, G.; Giambastiani, G.; Madec, D.; Pacini, B.; Poli, G. J. Organomet. Chem. 2003, 687, 291-300.
7. Poli, G.; Giambastiani, G.; Mordini, A. J. Org. Chem. 1999, 64, 2962-2965.
8. For reviews, see: (a) Tsuji, J. In Handbook of Organopalladium Chemistry for Organic Synthesis; Negishi, E.-I., Ed.; John Wiley & Sons: New York, 2002; pp 1669-1844. (b) Trost, B. M.; Van Vranken, D. L. Chem. Rev. 1996, 96, 395-422.
9. For reviews, see: (a) Tsuji, J. In Handbook of Organopalladium Chemistry for Organic Synthesis; Negishi, E.-I., Ed.; John Wiley & Sons: New York, 2002; pp 1669-1844. (b) Trost, B. M.; Van Vranken, D. L. Chem. Rev. 1996, 96, 395-422.
10. For generalities on phase-transfer catalysis, see: (a) Demlow, E. V.; Demlow, S. S. Phase Transfer Catalysis, 3rd ed.; VCH: Weinheim, 1993. (b) Goldberg, Y. Phase Transfer Catalysis: Selected Problems and Applications; Gordon & Breach Science Publishers: Reading, PA, 1992. (c) Starks, C. M.; Liotta, C. L.; Halpern, M. Phase Transfer Catalysis: Fundamentals, Applications, and Industrial Perspectives; Chapman & Hall: New York, 1994.
11. For generalities on phase-transfer catalysis, see: (a) Demlow, E. V.; Demlow, S. S. Phase Transfer Catalysis, 3rd ed.; VCH: Weinheim, 1993. (b) Goldberg, Y. Phase Transfer Catalysis: Selected Problems and Applications; Gordon & Breach Science Publishers: Reading, PA, 1992. (c) Starks, C. M.; Liotta, C. L.; Halpern, M. Phase Transfer Catalysis: Fundamentals, Applications, and Industrial Perspectives; Chapman & Hall: New York, 1994.
12. For generalities on phase-transfer catalysis, see: (a) Demlow, E. V.; Demlow, S. S. Phase Transfer Catalysis, 3rd ed.; VCH: Weinheim, 1993. (b) Goldberg, Y. Phase Transfer Catalysis: Selected Problems and Applications; Gordon & Breach Science Publishers: Reading, PA, 1992. (c) Starks, C. M.; Liotta, C. L.; Halpern, M. Phase Transfer Catalysis: Fundamentals, Applications, and Industrial Perspectives; Chapman & Hall: New York, 1994.
13. (a) Poli, G.; Madec, D. Chemtracts: Org. Chem. 2002, 15, 498-505.
14. (b) Nakoji, M.; Kanayama, T.; Okino, T.; Takemoto, Y. J. Org. Chem. 2002, 67, 7418-7423
15. (c) Nakoji, M.; Kanayama, T.; Okino, Y.; Takemoto, Y. Org. Lett. 2001, 3, 3329.
16. (d) Chen, G.; Deng, Y.; Gong, L.; Mi, A.; Cui, X.; Jiang, Y.; Choi, M. C. K.; Chan, A. S. C. Tetrahedron: Asymmetry 2001, 12, 1567.
17. For a review on the effect of halides in transition metal catalysis, see: Fagnou, K.; Lautens, M. Angew. Chem., Int. Ed. 2002, 41, 26-47.
18. Methyl groups in methyl esters are known to favor a planar s-cis conformation. See for example: Stereoelectronic Effects in Organic Chemistry: Deslongchamps, P., Ed.; Pergamon Press: Oxford, 1983.
19. 2Pd(OAc)]Na, which would result in a completely naked enolate instead of the zwitterionic form, in line with the observations of Amatore, Jutand, and co-workers: Amatore, C.; Jutand, A.; M'Barki, M. A.; Meyer, G.; Mottier, L. Eur. J. Inorg. Chem. 2001, 873-880. However, the reaction does not seem to be sensitive to the presence of halides; cf. entries 5 and 6, Table 1.
20. Deprotonation of the pronucleophile under biphasic PTC conditions is expected to take place in the interfacial region. (a) Makosza, M.; Krylowa, I. Tetrahedron 1999, 55, 6395-6402. (b) Mason, D. Magdassi, S.; Sasson, Y. J. Org. Chem. 1990, 55, 2714-2717. (c) Gobbi, A.; Landini, D.; Maia, A.; Petricci, S. J. Org. Chem. 1998, 63, 5356-5361. (d) Lygo, B.; Andrews, B. Acc. Chem. Res. 2004, 37, 518-525.
21. Deprotonation of the pronucleophile under biphasic PTC conditions is expected to take place in the interfacial region. (a) Makosza, M.; Krylowa, I. Tetrahedron 1999, 55, 6395-6402. (b) Mason, D. Magdassi, S.; Sasson, Y. J. Org. Chem. 1990, 55, 2714-2717. (c) Gobbi, A.; Landini, D.; Maia, A.; Petricci, S. J. Org. Chem. 1998, 63, 5356-5361. (d) Lygo, B.; Andrews, B. Acc. Chem. Res. 2004, 37, 518-525.
22. Deprotonation of the pronucleophile under biphasic PTC conditions is expected to take place in the interfacial region. (a) Makosza, M.; Krylowa, I. Tetrahedron 1999, 55, 6395-6402. (b) Mason, D. Magdassi, S.; Sasson, Y. J. Org. Chem. 1990, 55, 2714-2717. (c) Gobbi, A.; Landini, D.; Maia, A.; Petricci, S. J. Org. Chem. 1998, 63, 5356-5361. (d) Lygo, B.; Andrews, B. Acc. Chem. Res. 2004, 37, 518-525.
23. Deprotonation of the pronucleophile under biphasic PTC conditions is expected to take place in the interfacial region. (a) Makosza, M.; Krylowa, I. Tetrahedron 1999, 55, 6395-6402. (b) Mason, D. Magdassi, S.; Sasson, Y. J. Org. Chem. 1990, 55, 2714-2717. (c) Gobbi, A.; Landini, D.; Maia, A.; Petricci, S. J. Org. Chem. 1998, 63, 5356-5361. (d) Lygo, B.; Andrews, B. Acc. Chem. Res. 2004, 37, 518-525.
24. Norrby, P.-O.; Mader, M. M.; Vitale, M.; Prestat, G.; Poli, G. Organometallics 2003, 22, 1849-1855.
25. Jaguar 4.2; Schrödinger, Inc.: Portland, OR, 2000. See: http://www.schrodinger.com.
26. Marten, B.; Kim, K.; Cortis, C.; Friesner, R. A.; Murphy, R. B.; Ringnalda, M. N.; Sitkoff, D.; Honig, B. J. Phys. Chem. 1996, 100, 11775-11788.
27. Solvent model is essential for the success of the calculations; without it, the ring closure occurs without a barrier: Hagelin, H.; Åkermark, B.; Norrby, P.-O. Chem. Eur. J. 1999, 5, 902-909.
28. See for example: Trost, B. M.; Lee, C. B. J. Am. Chem. Soc. 2001, 123, 3671-3686.