First synthesis of metallated titanacyclopropenes

Synlett

Volumn , Issue 12, 1999, Pages 1939-1941

  Averbuj, Claudia ^a   Kaftanov, Julia ^a   Marek, Ilan ^a  

^a TECHNION ISRAEL INSTITUTE OF TECHNOLOGY   (Israel)

Author keywords

Alkenes; Alkynes; Bismetallic; Metallated titanacyclopropenes; Titanium(II)

Indexed keywords

CYCLOALKENE; PROPYLENE; TITANIUM DERIVATIVE;

ARTICLE; CHEMICAL BOND; CHEMICAL REACTION; CHEMICAL STRUCTURE; REACTION ANALYSIS; SYNTHESIS;

EID: 0032714743     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1999-2964     Document Type: Article

References (49)

1. a) J. Marek, J.F. Normant, Carbometallation Reactions in Metal-Catalyzed-Cross-Coupling Reactions in Cross-Coupling Reactions Eds. Stang, P.J.; Diederich, F. Wiley-VCH, Weinheim 1998, 271.
2. J. Barluenga, M.A. Rodriguez, P.J. Campos, G. Asensio, J. Am. Chem. Soc. 1988, 110, 5567 and references cited therein
3. a) T. Yoshida, E.I. Negishi, J. Am. Chem. Soc. 1981, 103, 1276.
4. b) E.I Negishi, Pure and Appl. Chem. 1981, 53, 2333.
5. a) C.E. Tucker, P. Knochel, J. Am. Chem. Soc. 1991, 113, 9888.
6. b) C.E. Tucker, B. Greve, W. Klein, P. Knochel, Organometallics 1994, 13, 94.
7. J.R. Waas, A.R. Sidduri, P. Knochel, Tetrahedron Lett. 1992, 33, 3717.
8. a) A. Pelter, E.M. Colclough, Tetrahedron 1995, 51, 811 and references cited therein.
9. b) M.P. Cooke, Jr. J. Org. Chem. 1994, 59, 2930.
10. a) E.I. Neghisi, H. Sawada, J.M. Tour, Y. Wei, J. Org. Chem. 1988, 53, 915.
11. a) M. Srebnik, L. Deloux, M. Sabat, J. Org. Chem. 1995, 69, 3276.
12. b) L. Deloux, M. Srebnik, J. Org. Chem. 1994, 59, 6871.
13. c) L. Deloux, E. Skrzypczak-Jankun, B.V. Cheesman, M. Srebnik,; M. Sabat, J. Am. Chem. Soc. 1994, 116, 10302.
14. a) M. Gaudemar, Compt. Rend. Acad. Sc., Paris série C 1971, 273, 1669.
15. b) Y. Frangin, M. Gaudemar, Compt. Rend. Acad. Sc., Paris série C 1974, 278, 885.
16. c) J. Auger, G. Courtois, L. Miginiac, J. Organomet. Chem, 1977, 133, 285.
17. a) I. Creton, I. Marek, J.F. Normant, Tetrahedron Lett. 1995, 36, 7451.
18. b) I. Creton, I. Marek, J.F. Normant, Synthesis 1996, 1499.
19. c) I. Creton, H. Rezaei, I. Marek, J.F. Normant, Tetrahedron Lett, 1999, 40, 1899.
20. K. Harada, H. Urabe, F. Sato, Tetrahedron Lett. 1995, 36, 3203.
21. For recent papers a) H. Urabe, T. Hamada, F. Sato, J. Am. Chem. Soc. 1999, 121, 2931.
22. b) Y. Takayama, S. Okamoto, F. Sato, J. Am. Chem. Soc. 1999, 121, 3559.
23. c) R. Mizojiri, H. Urabe, F. Sato, Tetrahedron Lett. 1999, 40, 2557.
24. d) H. Urabe, F. Sato, J. Am. Chem. Soc. 1999, 121, 1245
25. a) O. G. Kulinkovich, S.V. Sviridov, T.S. Vasilevski, T.S. Pritskaya, Zh. Org. Khim. 1989, 25, 2245.
26. b) O. G. Kulinkovich; T.S. Pritskaya, J. Org. Chem. USSR (Engl. Transl.) 1990, 25, 2027;
27. c) O.G. Kulinkovitch, S.V. Sviridov, D.A. Vasilevski Synthesis 1991, 234, and references cited therein.
28. a) J. Lee, J.D. Ha, J.K. Cha, J. Am. Chem. Soc. 1997, 119, 8127.
29. b) J. Lee, J.K. Cha J. Org. Chem. 1997, 62, 1584.
30. c) S.Y. Cho, J. Lee, R. K. Lammi, J.K. Cha J. Org. Chem. 1997, 62, 8235.
31. a) V. Chaplinski, A. de Meijere, Angew. Chem. Int. Ed. Engl. 1995, 34, 2545.
32. b) C.M. Williams, V. Chaplinski, P.R. Schreiner, A. de Meijere, Tetrahedron Lett. 1998, 39, 7695.
33. c) V. Chaplinski, H. Winsel, M. Kordes, A. de Meijere, Synlett 1997, 111.
34. d) C.M. Williams, A. de Meijere, J. Chem. Soc., Perkin Trans. 1 1998, 3699.
35. e) J. Lee, J.K. Cha, J. Org. Chem. 1997, 62, 1584.
36. Titanation of alkynyltin was already described, see: V. Launay, I. Baudet, J.P. Quintard, Synlett 1997, 821 and more recently, see ref. 12a. Zirconium mediated intramolecular coupling of terminal alkynes was also published J. Barluenga, R. Sanz, F.J. Fananas Chem. Eur. J. 1997, 3, 1324.
37. Titanation of alkynyltin was already described, see: V. Launay, I. Baudet, J.P. Quintard, Synlett 1997, 821 and more recently, see ref. 12a. Zirconium mediated intramolecular coupling of terminal alkynes was also published J. Barluenga, R. Sanz, F.J. Fananas Chem. Eur. J. 1997, 3, 1324.
38. Grignard Conditions (formation of the organometallic derivative and then introduction of the electrophile) as compared to Barbier Conditions (formation of the organometallic derivative in the presence of the electrophile).
39. This rearrangement was already reported for zirconocene derivatives; T. Takahashi, T. Fujimori, T. Seki, M. Saburi, Y. Uchida, C. J. Rousset, E. I. Negishi, J. Chem. Soc., Chem. Commun. 1990, 182.
40. 4.
41. All attempts to trap the intermediate 4 at low temperature were unsuccessful.
42. Equivalent reactions were described in the literature for the formation of vinylzirconium derivatives from zirconocenes and vinyl halides see T. Takahashi, M. Kotora, R. Fischer, Y. Nishihara, K. Nakajima J. Am. Chem. Soc. 1995, 117, 11039.
43. 11 into the chloroalkyne.
44. For the use of dialkylzirconocenes in synthesis, see the last review: E.I. Neghishi, T. Takahashi Bull. Chem. Soc. Jpn. 1998, 71, 755.
45. For the use of dialkyltitanocenes in synthesis, see S.L. Buchwald, R.B. Nielsen Chem. Rev. 1988, 88, 1047.
46. The balance being the starting material (21%) and the metalloalkyne (65%)
47. Whereas with 16 40% of the polymetallated olefin can be obtained (accompanied by the formation of high molecular weight products), the use of 17 gave only 10% of the desired metallated double bond (the major product being the starting material)
48. 4 and concentrated in vacuo to give a crude oil. Purification by chromatography (silica gel, hexane) afforded decene in 90% yield.
49. Until now, all our attempts to get crystals for X-Ray structure determination failed.