Unexpected consecutive propargyl-allenyl isomerization in nucleophilic trapping reactions of (arene)Cr(CO)3-substituted propargyl cations

Organometallics

Volumn 20, Issue 3, 2001, Pages 376-378

  Netz, Astrid ^a   Polborn, Kurt ^a   Müller, Thomas J J ^a  

^a UNIVERSITY OF MUNICH   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

NUCLEOPHILIC TRAPPING REACTION; PROPARGYLATED PHOSPHONIUM SALT; TRIPHENYLPHOSPHANE;

CATALYSIS; ISOMERIZATION; NEGATIVE IONS; SALTS; SOLUTIONS; STEREOCHEMISTRY; SUBSTITUTION REACTIONS; SYNTHESIS (CHEMICAL);

CHROMIUM COMPOUNDS;

EID: 0035809277     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om000921i     Document Type: Article

References (48)

1. (a) Semmelhack, M. F. Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: Oxford, U.K., 1995; Vol. 12, p 979.
2. (b) Davies, S. G.; McCarthy, T. D. Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: Oxford, U.K., 1995; Vol. 12, p 1039.
3. (a) Solladié-Cavallo, A. Polyhedron 1985, 4, 901.
4. (b) Jaouen, G. Pure Appl. Chem. 1986, 58, 597.
5. (c) Davies, S. G,; Donohoe, T. J. Synlett 1993, 323.
6. (a) Semmelhack, M. F.; Seufert, W.; Keller, L. J. Am. Chem. Soc. 1980, 102, 6584.
7. (b) Davies, S. G.; Coote S. J.; Goodfellow, C. L. In Advances in Metal-Organic Chemistry; Liesbeskind, L. S., Ed.; JAI Press: London 1991; Vol. 2, p 1.
8. For recent computational studies on the DFT level of theory see, e.g.: (a) Pfletschinger, A.; Dargel, T. K.; Bats, J. W.; Schmalz, H.-G.; Koch, W. Chem. Eur. J. 1999, 5, 537.
9. (b) Merlic, C. A.; Walsh, J. C.; Tantillo, D. J.; Houk, K. N. J. Am. Chem. Soc. 1999, 121, 3596.
10. (a) Semmelhack, M. F.; Zask, A. J. Am. Chem. Soc. 1983, 105, 2034.
11. (b) Uemura, M.; Minami, T.; Hayashi, Y. J. Chem. Soc., Chem. Commun. 1984, 1993.
12. (c) Uemura, M. In Advances in Metal-Organic Chemistry; Liebeskind, L. S. Ed.; JAI Press: London, 1991; Vol. 2, p. 195.
13. (d) Corey, E. J.; Helal, C. J. Tetrahedron Lett. 1996, 37, 4837.
14. (e) Schellhaas, K.; Schmalz, H.-G.; Bats, J. W. Chem. Eur. J. 1998, 4, 57.
15. (f) Schmalz, H.-G.; Siegel, S. In Transition Metals for Organic Synthesis; Beller, M., Bolm, C., Eds.; Wiley-VCH: Weinheim, Germany, 1998; Vol. 1, p 550.
16. (g) Schmalz, H.-G.; de Koning, C. B.; Bernicke, D.; Siegel, S.; Pfletschinger, A. Angew. Chem., Int. Ed. 1999, 38, 1620.
17. (a) Müller, T. J. J.; Lindner, H. J. Chem. Ber. 1996, 129, 607.
18. (b) Müller, T. J. J. Tetrahedron Lett. 1997, 38, 1025.
19. (c) Müller, T. J. J.; Ansorge, M.; Polborn, K. J. Organomet. Chem. 1999, 578, 252.
20. (d) Ansorge, M.; Müller, T. J. J. J. Organomet. Chem. 1999, 585, 174
21. (e) Müller, T. J. J. J. Organomet. Chem. 1999, 578, 95.
22. (f) Müller, T. J. J.; Netz, A.; Ansorge, M.; Schmälzlin, E.; Bräuchle, C.; Meerholz, K. Organometallics 1999, 18, 5066.
23. (a) Müller, T. J. J.; Netz, A. Organometallics 1998, 17, 3609.
24. (b) Müller, T. J. J.; Polborn K.Ansorge, M.; Polborn K. Organometallics 1998, 18, 3690.
25. (c) Müller, T. J. J.; Ansorge, M. Tetrahedron 1998, 54, 1457.
26. (d) Ansorge, M.; Polborn, K.; Müller, T. J. J. Eur. J. Inorg. Chem. 1999, 225.
27. Netz, A.; Müller, T. J. J. Organometallics 2000, 19, 1452.
28. (a) Müller, T. J. J.; Netz, A. Tetrahedron Lett. 1999, 40, 3145.
29. (b) Netz, A.; Müller, T. J. J. Tetrahedron 2000, 56, 4149.
30. (a) Murray, M. In Methoden zur Herstellung und Umwandlung von Allenen bzw. Kumulenen; Houben-Weyl, Eds.; Thieme: Stuttgart, Germany 1977; Vol. 5/2a, p 991.
31. For comprehensive Reviews of allene chemistry see, e.g.: (b) Taylor, D. R. Chem. Rev. 1967, 67, 317.
32. (c) Rutledge, T. F. Acetylenes and Allenes; Reinhold: New York, Amsterdam, London, 1969, Parts 1-3.
33. (d) Brady, W. T. In The Chemistry of Ketenes, Allenes and Related Compounds; Patai, S., Ed.; Wiley: Chichester, New York, Brisbane, Toronto, 1980; Part 1, p 298.
34. (e) Hopf; H. In The Chemistry of Ketenes, Allenes and Related Compounds; Patai, S., Ed.; Wiley: Chichester, New York, Brisbane, Toronto, 1980; Part 2, p 779.
35. (f) Smadja, W. Chem. Rev. 1983, 83, 263.
36. (g) Pasto, D. J. Tetrahedron 1984, 40, 2805.
37. (h) Schuster, H. F.; Coppola, G. M. Allenes in Organic Synthesis; Wiley: Chichester, New York, Brisbane, Toronto, 1984.
38. For a comprehensive overview see, e.g.: Modern Acetylene Chemistry; Stang, P. J., Diederich, F., Eds.; VCH: Weinheim, Germany, 1995.
39. Barry; B. J.; Beale, W. J.; Carr, M. D.; Hei, S.-K.; Reid, I. J. Chem. Soc., Chem. Commun. 1973, 177.
40. Synthesis of the allenyl phosphonium salts 3: To a solution of 1 equiv (0.5 mmol) of the acetate 1 in 5 mL of dry dichloromethane was added dropwise 1.3 equiv of TMSOTf at -78°C. Immediately a deeply colored solution of the propargyl cation 2 was formed, which was stirred at that temperature for 40-60 min. To this reaction mixture was then added a solution of 2.2 equiv of triphenylphosphane in 3 mL of dichloromethane at -78°C. The reaction can be followed by a color change from deep purple to yellow. After 55-65 min subsequently 20 mL of diethyl ether and 20 mL of water were added and the external cooling was removed. After extraction of the aqueous phase with dichloromethane (2 × 25 mL) the combined organic layers were dried with magnesium sulfate and filtered and the solvents were evaporated in vacuo. The residue was dried in vacuo and triturated with diethyl ether to give as a yellow crystalline soid. Further purification was achieved by recrystallization from dichloromethane/diethyl ether. 3a: yield 270 mg (69%); yellow crystals; mp > 185°C dec. 3b: yield 270 mg (73%, dr = 61:39); yellow crystals (dichloromethane/diethyl ether); mp > 183°C dec. 3c: yield 219 mg (77%, dr = 60:40); yellow foam.
41. Quantum CAChe 3.0 Program, Oxford Molecular Group, 1997.
42. 13C NMR Spektroskopie; Georg Thieme Verlag: Stuttgart, New York, 1984, p 129.
43. Tebby, J. C. Phosphorus-31 Nuclear Magnetic Resonance Data; CRC Press: Boca Raton, FL, 1980.
44. Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as Suppementary Publication Nos. CCDC-151549 (3a) and CCDC-151548 (3b). Copies of the data can be obtained free of charge on application to the CCDC, 12 Union Road Cambridge CB2 1EZ, U.K. (fax, + 44-1223/336-033; e-mail, deposit@ccdc.cam.ac.uk).
45. The crystals suitable for the X-ray structure analysis of 3b showed a modest enrichment of the major diastereomer (dr = 70.5: 29.5), as determined from the displacement of the ortho methyl group in positions C5 and C9 with a distribution of 70.5% to 29.5%.
46. Müller T. J. J.; Ansorge, M. Chem. Ber./Recl. 1997, 130, 1135.
47. For a base-catalyzed isomerization of propargyl phosphonium salts see, e.g.: Khachatryan, R. A.; Mkrtchyan, G. A.; Kinoyan, F. S.; Indzhikyan, M. G. J. Gen. Chem. USSR (Engl. Transl.) 1986, 207-208.
48. For stable propargyl ylides see, e.g.: Pommer, H. Angew. Chem. 1960, 72, 811.