Carbenoid chain reactions: Substitutions by organolithium compounds at unactivated 1-chloro-1-alkenes

Journal of the American Chemical Society

Volumn 128, Issue 46, 2006, Pages 14845-14853

  Knorr, Rudolf ^a   Pires, Claudio ^a   Behringer, Claudia ^a   Menke, Thomas ^a   Freudenreich, Johannes ^a   Rossmann, Eva C ^a   Böhrer, Petra ^a  

^a UNIVERSITY OF MUNICH   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSTS; CONCENTRATION (PROCESS); REACTION KINETICS; SUBSTITUTION REACTIONS; TRANSITION METALS;

ALKYLIDENECARBENOID; CHAIN CARRIER;

LITHIUM COMPOUNDS;

2 (CHLOROMETHYLIDENE) 1,1,3,3 TETRAMETHYLINDAN DERIVATIVE; 2,4,6 TRI TERT BUTYLPHENYLLITHIUM; 2,6 DIMETHYLPHENYLLITHIUM; ALKENE DERIVATIVE; BUTYLLITHIUM; CARBENOID; INDAN DERIVATIVE; LITHIUM DERIVATIVE; METHYLLITHIUM; ORGANOLITHIUM COMPOUND; UNCLASSIFIED DRUG;

ARTICLE; CATALYST; CHEMICAL REACTION KINETICS; CONCENTRATION RESPONSE; CROSS COUPLING REACTION; METAL BINDING; NUCLEAR MAGNETIC RESONANCE; STEADY STATE; STEREOCHEMISTRY; SUBSTITUTION REACTION;

EID: 33845222297     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0649116     Document Type: Article

References (81)

1. Modena, G. Acc. Chem. Res. 1971, 4, 73-80.
2. Glukhovtsev, M. N.; Pross, A.; Radom, L. J. Am. Chem. Soc. 1994, 116, 5961-5962.
3. Rappoport, Z. Acc. Chem. Res. 1992, 25, 474-479, and cited literature.
4. (a) Knorr, R. Chem. Rev. 2004, 104, 3795-3849.
5. (b) Knorr, R. Chem. Rev. 2004, 104, 3817-3818.
6. (c) Knorr, R. Chem. Rev. 2004, 104, 3831.
7. (d) Knorr, R. Chem. Rev. 2004, 104, 3832.
8. (e) Knorr, R. Chem. Rev. 2004, 104, 3833.
9. (f) Knorr, R. Chem. Rev. 2004, 104, 3842.
10. (g) Knorr, R. Chem. Rev. 2004, 104, 3843.
11. (h) Knorr, R. Chem. Rev. 2004, 104, 3841
12. (i) Knorr, R. Chem. Rev. pp 3823-3825.
13. (j) Knorr, R. Chem. Rev. 2004, 104, 3805.
14. (k) Knorr, R. Chem. Rev. 2004, 104, 3822.
15. (l) Knorr, R. Chem. Rev. 2004, 104, 3829.
16. Carbenoids carry both a metal cation and a nucleofugal group at the same carbon atom: Köbrich, G. Angew. Chem. 1972, 84, 557-570, first footnote therein;
17. Angew. Chem., Int. Ed. Engl. 1972, 11, 473-485.
18. Nomenclature: Stang, P. J. Acc. Chem. Res. 1982, 15, 348-354.
19. Compound 18b in ref 9.
20. Knorr, R.; Mehlstäubl, J.; Bohrer, P. Chem. Ber. 1989, 122, 1791-1793 and refs therein.
21. Knorr, R.; Freudenreich, J.; von Roman, T.; Mehlstäubl, J.; Böhrer, P. Tetrahedron 1993, 49, 8837-8854.
22. Details are given in the Supporting Information.
23. Taguchi, H.; Yamamoto, H.; Nozaki, H. J. Am. Chem. Soc. 1974, 96, 3010-3011.
24. Köbrich, G.; Grosser, J.; Werner, W. Chem. Ber. 1973, 106, 2610-2619.
25. Hofmann, P.; Perez-Moya, L. A.; Kain, I. Synthesis 1986, 43-44.
26. α missing).
27. Most of the yields (up to 85% of 4) were determined in small-scale runs (0.1-1 mmol) under nonoptimized conditions.
28. 1/2 increases with decreasing initial concentrations [RLi], which varied by factors up to three here.
29. 2O at 0°C: Schlosser, M.; Ladenberger, V. Chem. Ber. 1967, 100, 3877-3892.
30. 3C-(t-Bu)C=C=CD-Br by: Schiavelli, M. D.; Ellis, D. E. J. Am. Chem. Soc. 1973, 95, 7916-7917.
31. 4a much slower than the substitution reaction and hence unlikely.
32. Knorr, R. and co-workers, unpublished.
33. 55 in high yields.
34. Knorr, R.; Freudenreich, J.; Polborn, K.; Nöth, H.; Linti, G. Tetrahedron 1994, 50, 5845-5860.
35. 10 through competition of 2a with 2b for a substoichiometric amount of MeLi.
36. Curtin, D. Y.; Richardson, W. H. J. Am. Chem. Soc. 1959, 81, 4719-4728, on p 4721.
37. Günther, H.; Bothner-By, A. A. Chem. Ber. 1963, 96, 3112-3119, on p 3115.
38. Cunico, R. F.; Han, Y.-K. J. Organomet. Chem. 1978, 162, 1-16, on p 3.
39. 4a fast at room temperature.
40. Schlosser, M. Struktur und Reaktivität polarer Organometalle; Springer-Verlag: NewYork, 1973; p 126.
41. Wardell, J. L. In Comprehensive Organometallic Chemistry; Wilkinson, G., Stone, F. A. G., Abel, E. W., Eds.; Pergamon: Oxford 1982; Vol. 1, p 50.
42. Hässig, R.; Seebach, D. Helv. Chim. Acta 1983, 66, 2269-2273.
43. Bauer, W.; Seebach, D. Helv. Chim. Acta 1984, 67, 1972-1988.
44. Antipin, I. S.; Gareyev, R. F.; Vedernikov, A. N.; Konovalov, A. I. J. Phys. Org. Chem. 1994, 7, 181-191;
45. Chem. Abstr. 1994, 121, 255158s.
46. a ≤ 21.2 in water: Kresge, A. J.; Pruszynski, P.; Stang, P. J.; Williamson, B. L. J. Org. Chem. 1991, 56, 4808-4811.
47. Several of the decelerations observed in this system are too large to be ascribed to hypothetic mixed aggregates of PhC≡CLi with RLi causing a retardation of noncarbenoid substitution processes. Such aggregates are weakly bound and usually hard to detect as the components of very mobile equilibria in solution. An elucidation of their role would require extended series of precise rate measurements which are beyond the scope of this work.
48. Zweifel, G.; Rajagopalan, S. J. Am. Chem. Soc. 1985, 107, 700-701
49. Brandsma, L.; Hommes, H.; Verkruijsse, V. D.; Kos, A. J.; Neugebauer, W.; Baumgärtner, W.; Schleyer, P. v. R. Recl. Trav. Chim. Pays-Bas 1988, 107, 286-295.
50. Seebach, D.; Hässig, R.; Gabriel, J. Helv. Chim. Acta 1983, 66, 308-337.
51. McGarrity, J. F.; Ogle, C. A. J. Am. Chem. Soc. 1985, 107, 1805-1810.
52. Heinzer, J.; Oth, J. F. M.; Seebach, D. Helv. Chim. Acta 1985, 68, 1848-1862.
53. Bauer, W.; Clark, T.; Schleyer, P. v. R. J. Am. Chem. Soc. 1987, 109, 970-977.
54. (a) Compound 6 in ref 9.
55. (b) Compound 43 in ref 9.
56. Köbrich, G.; Ansari, F. Chem. Ber. 1967, 100, 2011-2020, on p 2014.
57. Bauer, W.; Winchester, W.; Schleyer, P. v. R. Organometallics 1987, 6, 2371-2379.
58. (a) Reich, H. J.; Green, D. P.; Phillips, N. H. J. Am. Chem. Soc. 1989 111, 3444-3445.
59. (b) Reich, H. J.; Green, D. P.; Phillips, N. H. J. Am. Chem. Soc. 1991, 113, 1414-1416.
60. Gerold, A.; Jastrzebski, J. T. B. H.; Kronenburg, C. M. P.; Krause, N.; van Koten, G. Angew. Chem. 1997, 109, 778-780;
61. Angew. Chem., Int. Ed. Engl. 1997, 36, 755-757.
62. Knorr, R.; Hoang, T. P.; Nöth, H.; Linti, G. Organometallics 1992, 11, 2669-2673.
63. Knorr, R.; Lattke, E.; Räpple, E. Liebigs Ann. Chem. 1980, 1207-1215.
64. Reich, H. J.; Sikorski, W. H.; Gudmundsson, B. Ö.; Dykstra, R. R. J. Am. Chem. Soc. 1998, 120, 4035-4036.
65. Wehman, E.; Jastrzebski, J. T. B. H.; Ernsting, J.-M.; Grove, D. M.; van Koten, G. J. Organomet. Chem. 1988, 353, 133-143.
66. Fraenkel, G.; Subramanian, S.; Chow, A. J. Am. Chem. Soc. 1995, 117, 6300-6307.
67. Crystal structure: Maetzke, T.; Seebach, D. Helv. Chim. Acta 1989, 72, 624-630.
68. Watanabe, S.; Kawashima, T.; Tokitoh, N.; Okazaki, R. Bull. Chem. Soc. Jpn. 1995, 68, 1437-1448.
69. 2O, as judged from the stoichiometries (1:1 and 2:1, respectively) reported by: Molines, H.; Normant, J.-M.; Wakselman, C. Tetrahedron Lett. 1974, 951-954, Tableau I therein.
70. Köbrich, G.; Merkel, D.; Thiem, K.-W. Chem. Ber. 1972, 105, 1683-1693.
71. Hartzler, H. D. J. Am. Chem. Soc. 1964, 86, 526-527.
72. Fitjer, L.; Kliebisch, U.; Wehle, D.; Modaressi, S. Tetrahedron Lett. 1982 23, 1661-1664.
73. Knorr, R.; Pires, C.; Freudenreich, J. In preparation.
74. Knorr, R.; von Roman, T.; Freudenreich, J.; Hoang, T. P.; Mehlstäubl, J.; Böhrer, P.; Stephenson, D. S.; Huber, H.; Schubert, B. Magn. Reson. Chem. 1993, 31, 557-565.
75. Clark, H. A.; Gordon, A. F.; Young, C. W.; Hunter, M. J. J. Am. Chem. Soc. 1951, 73, 3798-3803.
76. Allred, A. L.; Bush, L. W. J. Am. Chem. Soc. 1968, 90, 3352-3360.
77. Noltes, J. G.; van der Kerk, G. J. M. Recl. Trav. Chim. Pays-Bas 1962, 81, 565-577, on p 569.
78. Haubold, W.; Herdtle, J.; Gollinger, W.; Einholz, W. J. Organomet. Chem. 1986, 315, 1-8.
79. Cowley, A. H.; Norman, N. C.; Pakulski, M. Inorg. Synth. 1990, 27, 235-237.
80. Betts, E. E.; Barclay, L. R. C. Can. J. Chem. 1955, 33, 1768-1774.
81. Pearson, D. E.; Frazer, M. G.; Frazer, V. S.; Washburn, L. C. Synthesis 1976, 621-623.