Palladium-catalyzed elimination reaction of acyclic (E)-allylic acetates: The stereochemistry elucidated by "syn-effect"

Chemistry Letters

Volumn 34, Issue 2, 2005, Pages 256-257

  Takenaka, Hiroyuki ^a   Ukaji, Yutaka ^a   Inomata, Katsuhiko ^a  

^a KANAZAWA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ACETIC ACID DERIVATIVE; ALKADIENE; ALLYL COMPOUND; BASE; FUNCTIONAL GROUP; PALLADIUM;

ARTICLE; CATALYSIS; CHEMICAL INTERACTION; ELIMINATION REACTION; STEREOCHEMISTRY;

EID: 17844400801     PISSN: 03667022     EISSN: None     Source Type: Journal    
DOI: 10.1246/cl.2005.256     Document Type: Article

References (24)

1. a) J. Tsuji, "Palladium Reagents and Catalysts," John Wiley & Sons, Ltd., Chichester (1995), pp 356-363.
2. b) I. Shimizu, "Handbook of Organopalladium Chemistry for Organic Synthesis," ed. by E. Negishi, John Wiley & Sons, Inc., New York (2002), Vol. 2, Chap. V. 2.5.1.
3. The reaction pathway of elimination reaction of cyclic allylic compounds to the corresponding 1,3-dienes has been discussed, and not only syn-β-elimination but also anti-elimination was proposed to be taken place, especially in the presence of a base, a) E. Keinan, S. Kumar, V. Dangur, and J. Vaya, J. Am. Chem. Soc., 116, 11151 (1994). b) P. G. Andersson and S. Schab, Organometallics, 14, 1 (1995). c) J. M. Takacs, E. C. Lawson, and F. Clement, J. Am. Chem. Soc., 119, 5956 (1997).
4. The reaction pathway of elimination reaction of cyclic allylic compounds to the corresponding 1,3-dienes has been discussed, and not only syn-β-elimination but also anti-elimination was proposed to be taken place, especially in the presence of a base, a) E. Keinan, S. Kumar, V. Dangur, and J. Vaya, J. Am. Chem. Soc., 116, 11151 (1994). b) P. G. Andersson and S. Schab, Organometallics, 14, 1 (1995). c) J. M. Takacs, E. C. Lawson, and F. Clement, J. Am. Chem. Soc., 119, 5956 (1997).
5. The reaction pathway of elimination reaction of cyclic allylic compounds to the corresponding 1,3-dienes has been discussed, and not only syn-β-elimination but also anti-elimination was proposed to be taken place, especially in the presence of a base, a) E. Keinan, S. Kumar, V. Dangur, and J. Vaya, J. Am. Chem. Soc., 116, 11151 (1994). b) P. G. Andersson and S. Schab, Organometallics, 14, 1 (1995). c) J. M. Takacs, E. C. Lawson, and F. Clement, J. Am. Chem. Soc., 119, 5956 (1997).
6. A. Shibayama, T. Nakamura, T. Asada, T. Shintani, Y. Ukaji, H. Kinoshita, and K. Inomata, Bull. Chem. Soc. Jpn., 70, 381 (1997).
7. The "syn-effect" is herein defined as an effect which stabilizes the syn-conformation against the steric hindrance.
8. Related studies on the "syn-effect"; a) T. Hirata, Y. Sasada, T. Ohtani, T. Asada, H. Kinoshita, H. Senda, and K. Inomata, Bull. Chem. Soc. Jpn., 65, 75 (1992). b) T. Nakamura, S. K. Guha, Y. Ohta, D. Abe, Y. Ukaji, and K. Inomata, Bull. Chem. Soc. Jpn., 75, 2031 (2002). c) S. K. Guha, A. Shibayama, D. Abe, Y. Ukaji, and K. Inomata, Chem. Lett., 32, 778 (2003). d) S. K. Guha, Y. Ukaji, and K. Inomata, Chem. Lett., 32, 1158 (2003). e) S. K. Guha, A. Shibayama, D. Abe, M. Sakaguchi, Y. Ukaji, and K. Inomata, Bull. Chem. Soc. Jpn., 77, 2147 (2004). See also references cited therein.
9. Related studies on the "syn-effect"; a) T. Hirata, Y. Sasada, T. Ohtani, T. Asada, H. Kinoshita, H. Senda, and K. Inomata, Bull. Chem. Soc. Jpn., 65, 75 (1992). b) T. Nakamura, S. K. Guha, Y. Ohta, D. Abe, Y. Ukaji, and K. Inomata, Bull. Chem. Soc. Jpn., 75, 2031 (2002). c) S. K. Guha, A. Shibayama, D. Abe, Y. Ukaji, and K. Inomata, Chem. Lett., 32, 778 (2003). d) S. K. Guha, Y. Ukaji, and K. Inomata, Chem. Lett., 32, 1158 (2003). e) S. K. Guha, A. Shibayama, D. Abe, M. Sakaguchi, Y. Ukaji, and K. Inomata, Bull. Chem. Soc. Jpn., 77, 2147 (2004). See also references cited therein.
10. Related studies on the "syn-effect"; a) T. Hirata, Y. Sasada, T. Ohtani, T. Asada, H. Kinoshita, H. Senda, and K. Inomata, Bull. Chem. Soc. Jpn., 65, 75 (1992). b) T. Nakamura, S. K. Guha, Y. Ohta, D. Abe, Y. Ukaji, and K. Inomata, Bull. Chem. Soc. Jpn., 75, 2031 (2002). c) S. K. Guha, A. Shibayama, D. Abe, Y. Ukaji, and K. Inomata, Chem. Lett., 32, 778 (2003). d) S. K. Guha, Y. Ukaji, and K. Inomata, Chem. Lett., 32, 1158 (2003). e) S. K. Guha, A. Shibayama, D. Abe, M. Sakaguchi, Y. Ukaji, and K. Inomata, Bull. Chem. Soc. Jpn., 77, 2147 (2004). See also references cited therein.
11. Related studies on the "syn-effect"; a) T. Hirata, Y. Sasada, T. Ohtani, T. Asada, H. Kinoshita, H. Senda, and K. Inomata, Bull. Chem. Soc. Jpn., 65, 75 (1992). b) T. Nakamura, S. K. Guha, Y. Ohta, D. Abe, Y. Ukaji, and K. Inomata, Bull. Chem. Soc. Jpn., 75, 2031 (2002). c) S. K. Guha, A. Shibayama, D. Abe, Y. Ukaji, and K. Inomata, Chem. Lett., 32, 778 (2003). d) S. K. Guha, Y. Ukaji, and K. Inomata, Chem. Lett., 32, 1158 (2003). e) S. K. Guha, A. Shibayama, D. Abe, M. Sakaguchi, Y. Ukaji, and K. Inomata, Bull. Chem. Soc. Jpn., 77, 2147 (2004). See also references cited therein.
12. Related studies on the "syn-effect"; a) T. Hirata, Y. Sasada, T. Ohtani, T. Asada, H. Kinoshita, H. Senda, and K. Inomata, Bull. Chem. Soc. Jpn., 65, 75 (1992). b) T. Nakamura, S. K. Guha, Y. Ohta, D. Abe, Y. Ukaji, and K. Inomata, Bull. Chem. Soc. Jpn., 75, 2031 (2002). c) S. K. Guha, A. Shibayama, D. Abe, Y. Ukaji, and K. Inomata, Chem. Lett., 32, 778 (2003). d) S. K. Guha, Y. Ukaji, and K. Inomata, Chem. Lett., 32, 1158 (2003). e) S. K. Guha, A. Shibayama, D. Abe, M. Sakaguchi, Y. Ukaji, and K. Inomata, Bull. Chem. Soc. Jpn., 77, 2147 (2004). See also references cited therein.
13. δ double bond was discussed.
14. W. L. Steffen and G. J. Palenik, Inorg. Chem., 15, 2432 (1976).
15. 15
16. The anti-β-elimination via E could be ruled out because (E)-diene is anticipated to be produced selectively due to steric repulsion between substituents.
17. a) T. Laube and H. U. Stilz, J. Am. Chem. Soc., 109, 5876 (1987).
18. b) T. Laube and T.-K. Ha, J. Am. Chem. Soc., 110, 5511 (1988).
19. c) P. R. Rablen, R. W. Hoffmann, D. A. Hrovat, and W. T. Borden, J. Chem. Soc., Perkin Trans. 2, 1999, 1719.
20. Y. Apeloig, P. v. R. Schleyer, and J. A. Pople, J. Am. Chem. Soc., 99, 5901 (1977).
21. 3,5
22. 12 might relatively more contribute to the "syn-effect" of the BnS group.
23. V. D. Makhaev, Z. M. Dzhabieva, S. V. Konovalikhin, O. A. D'yachenko, and G. P. Belov, Russ. J. Coord. Chem., 22, 563 (1996).
24. N. Koga, S. Obara, K. Kitaura, and K. Morokuma, J. Am. Chem. Soc., 107, 7109 (1985).