X-ray crystal structure of a zinc carbenoid cyclopropanating reagent: The IZnCH2I·18-crown-6 and benzo-18-crown-6 complexes

Journal of the American Chemical Society

Volumn 118, Issue 28, 1996, Pages 6792-6793

  Charette, André B ^a   Marcoux, Jean François ^a   Bélanger Gariépy, Francine ^a  

^a UNIVERSITÉ DE MONTRÉAL   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

CROWN ETHER DERIVATIVE; PHENOL; ZINC COMPLEX;

ARTICLE; COMPLEX FORMATION; DRUG STRUCTURE; NUCLEAR MAGNETIC RESONANCE; PHOTOCHEMISTRY;

EID: 0029883097     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja953816m     Document Type: Article

References (41)

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9. This reagent has also been extensively used for homologation reactions in synthesis: (a) Knochel, P.; Singer, R. D. Chem. Rev. 1993, 93, 2117-2188. (b) Motherwell, W. B.; Nutley, C. J. Contemp. Org. Synth. 1994, 1, 219-241.
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15. Charette, A. B.; Marcoux, J.-F. J. Am. Chem. Soc. 1996, 118, 4539-4549.
16. For a review, see: Charette, A. B.; Marcoux, J.-F. Synlett. 1995, 1197-1207.
17. w = 0.1688 for 5628 reflections with I > 2σ(I). A full description of the structure is provided in the supporting information.
18. 2Zn (100 μL, 0.98 mmol) under argon. The resulting mixture was stirred at room temperature until the complete disappearance of the brown color and was recooled to -40 °C. Diiodomethane (79 μL, 0.98 mmol) was then slowly added, and the clear solution was rapidly warmed to 25 °C. Suitable crystals were slowly formed upon standing at room temperature.
19. For examples of pentacoordinated zinc complexes, see: (a) Ansell, C. W. G.; Dancey, K. P.; McPartlin, M.; Tasker, P. A.; Lindoy, L. F. J. Chem. Soc., Dalton Trans. 1983, 1789-1791. (b) Drew, M. G. B.; Hollis, S. J. Chem. Soc., Dalton Trans. 1978, 511-516. Markies, P. R.; Schat, G.; Akkerman, O. S.; Bickelhaupt, F.; Spek, A. L. J. Organomet. Chem. 1992, 430, 1-13.
20. For examples of pentacoordinated zinc complexes, see: (a) Ansell, C. W. G.; Dancey, K. P.; McPartlin, M.; Tasker, P. A.; Lindoy, L. F. J. Chem. Soc., Dalton Trans. 1983, 1789-1791. (b) Drew, M. G. B.; Hollis, S. J. Chem. Soc., Dalton Trans. 1978, 511-516. Markies, P. R.; Schat, G.; Akkerman, O. S.; Bickelhaupt, F.; Spek, A. L. J. Organomet. Chem. 1992, 430, 1-13.
21. For examples of pentacoordinated zinc complexes, see: (a) Ansell, C. W. G.; Dancey, K. P.; McPartlin, M.; Tasker, P. A.; Lindoy, L. F. J. Chem. Soc., Dalton Trans. 1983, 1789-1791. (b) Drew, M. G. B.; Hollis, S. J. Chem. Soc., Dalton Trans. 1978, 511-516. Markies, P. R.; Schat, G.; Akkerman, O. S.; Bickelhaupt, F.; Spek, A. L. J. Organomet. Chem. 1992, 430, 1-13.
22. Recent examples of threaded structure of 18-crown-6-complexes: (a) Pajerski, A. D.; BergStresser, G. L.; Parvez, M.; Richey, H. G., Jr. J. Am. Chem. Soc. 1988, 110, 4844-4845. (b) Paige, C. R.; Richardson, M. F. Can. J. Chem. 1984, 62, 332-335. Kawasaki, Y.; Matsuura, Y. Chem. Lett. 1984, 155-158. Pears, D. A.; Stoddart, J. F.; Crosby, J.; Allwood, B. L.; Williams, D. J. Acta Crystallogr., Sect. C 1986, 42, 51-53. (e) Hazell, A. Acta Crystallogr., Sect. C 1988, 44, 88-92. (f) Drew, M. G. B.; Lee, K. C.; Mok, K. F. Inorg. Chim. Acta 1989, 155, 39-43.
23. Recent examples of threaded structure of 18-crown-6-complexes: (a) Pajerski, A. D.; BergStresser, G. L.; Parvez, M.; Richey, H. G., Jr. J. Am. Chem. Soc. 1988, 110, 4844-4845. (b) Paige, C. R.; Richardson, M. F. Can. J. Chem. 1984, 62, 332-335. Kawasaki, Y.; Matsuura, Y. Chem. Lett. 1984, 155-158. Pears, D. A.; Stoddart, J. F.; Crosby, J.; Allwood, B. L.; Williams, D. J. Acta Crystallogr., Sect. C 1986, 42, 51-53. (e) Hazell, A. Acta Crystallogr., Sect. C 1988, 44, 88-92. (f) Drew, M. G. B.; Lee, K. C.; Mok, K. F. Inorg. Chim. Acta 1989, 155, 39-43.
24. Recent examples of threaded structure of 18-crown-6-complexes: (a) Pajerski, A. D.; BergStresser, G. L.; Parvez, M.; Richey, H. G., Jr. J. Am. Chem. Soc. 1988, 110, 4844-4845. (b) Paige, C. R.; Richardson, M. F. Can. J. Chem. 1984, 62, 332-335. Kawasaki, Y.; Matsuura, Y. Chem. Lett. 1984, 155-158. Pears, D. A.; Stoddart, J. F.; Crosby, J.; Allwood, B. L.; Williams, D. J. Acta Crystallogr., Sect. C 1986, 42, 51-53. (e) Hazell, A. Acta Crystallogr., Sect. C 1988, 44, 88-92. (f) Drew, M. G. B.; Lee, K. C.; Mok, K. F. Inorg. Chim. Acta 1989, 155, 39-43.
25. Recent examples of threaded structure of 18-crown-6-complexes: (a) Pajerski, A. D.; BergStresser, G. L.; Parvez, M.; Richey, H. G., Jr. J. Am. Chem. Soc. 1988, 110, 4844-4845. (b) Paige, C. R.; Richardson, M. F. Can. J. Chem. 1984, 62, 332-335. Kawasaki, Y.; Matsuura, Y. Chem. Lett. 1984, 155-158. Pears, D. A.; Stoddart, J. F.; Crosby, J.; Allwood, B. L.; Williams, D. J. Acta Crystallogr., Sect. C 1986, 42, 51-53. (e) Hazell, A. Acta Crystallogr., Sect. C 1988, 44, 88-92. (f) Drew, M. G. B.; Lee, K. C.; Mok, K. F. Inorg. Chim. Acta 1989, 155, 39-43.
26. Recent examples of threaded structure of 18-crown-6-complexes: (a) Pajerski, A. D.; BergStresser, G. L.; Parvez, M.; Richey, H. G., Jr. J. Am. Chem. Soc. 1988, 110, 4844-4845. (b) Paige, C. R.; Richardson, M. F. Can. J. Chem. 1984, 62, 332-335. Kawasaki, Y.; Matsuura, Y. Chem. Lett. 1984, 155-158. Pears, D. A.; Stoddart, J. F.; Crosby, J.; Allwood, B. L.; Williams, D. J. Acta Crystallogr., Sect. C 1986, 42, 51-53. (e) Hazell, A. Acta Crystallogr., Sect. C 1988, 44, 88-92. (f) Drew, M. G. B.; Lee, K. C.; Mok, K. F. Inorg. Chim. Acta 1989, 155, 39-43.
27. Recent examples of threaded structure of 18-crown-6-complexes: (a) Pajerski, A. D.; BergStresser, G. L.; Parvez, M.; Richey, H. G., Jr. J. Am. Chem. Soc. 1988, 110, 4844-4845. (b) Paige, C. R.; Richardson, M. F. Can. J. Chem. 1984, 62, 332-335. Kawasaki, Y.; Matsuura, Y. Chem. Lett. 1984, 155-158. Pears, D. A.; Stoddart, J. F.; Crosby, J.; Allwood, B. L.; Williams, D. J. Acta Crystallogr., Sect. C 1986, 42, 51-53. (e) Hazell, A. Acta Crystallogr., Sect. C 1988, 44, 88-92. (f) Drew, M. G. B.; Lee, K. C.; Mok, K. F. Inorg. Chim. Acta 1989, 155, 39-43.
28. For selected examples of noncentrosymmetric complexes derived from 18-crown-6, see: (a) Doxsee, K. M.; Hagadorn, J. R.; Weakley, T. J. R. Inorg. Chem. 1994, 33, 2600-2606. (b) Atwood, J. L.; Bott, S. G.; Harvery, S.; Junk, P. C. Organometallic 1994, 13, 4151-4152. Willey, G. R.; Lakin, M. T.; Alcock, N. W. J. Chem. Soc., Chem. Commun. 1992, 1619-1620.
29. For selected examples of noncentrosymmetric complexes derived from 18-crown-6, see: (a) Doxsee, K. M.; Hagadorn, J. R.; Weakley, T. J. R. Inorg. Chem. 1994, 33, 2600-2606. (b) Atwood, J. L.; Bott, S. G.; Harvery, S.; Junk, P. C. Organometallic 1994, 13, 4151-4152. Willey, G. R.; Lakin, M. T.; Alcock, N. W. J. Chem. Soc., Chem. Commun. 1992, 1619-1620.
30. For selected examples of noncentrosymmetric complexes derived from 18-crown-6, see: (a) Doxsee, K. M.; Hagadorn, J. R.; Weakley, T. J. R. Inorg. Chem. 1994, 33, 2600-2606. (b) Atwood, J. L.; Bott, S. G.; Harvery, S.; Junk, P. C. Organometallic 1994, 13, 4151-4152. Willey, G. R.; Lakin, M. T.; Alcock, N. W. J. Chem. Soc., Chem. Commun. 1992, 1619-1620.
31. (a) Dekker, J.; Boersma, J.; van der Kerk, G. J. M. J. Chem. Soc., Chem. Commun. 1983, 553-555.
32. (b) Dekker, J.; Budzelaar, P. H. M.; Boersma, J.; van der Kerk, G. J. M.; Spek, A. L. Organometallics 1984, 3, 1403-1407.
33. (c) Bellus, D.; Klingen, B.; Lang, R. W.; Rihs, G. J. Organometal. Chem. 1988, 339, 17-22.
34. (d) Gruter, G.-J. M.; Akkerman, O. S.; Bickelhaupt, F.; Smeets, W. J. J.; Spek, A. L. Recl. Trav. Chim. Pays-Bas 1993, 112, 425.
35. 0.25. The bond angles Zn-C-I observed for this complex are 119.0(8)° and 119.4(10)°. The details of this structure are provided in the supporting information. The wider torsion angles may be a consequence of the threaded structure of the complexes.
36. 2-benzo-18-crown-6 complex during the data collection. Although ethylene formation could not be detected by X-ray, the crystals swelled even at 173 K.
37. To the best of our knowledge, there is only one other X-ray crystal structure of a benzo-18-crown-6 complex: Simonov, Y. A.; Dvorkin, A. A.; Fonar, M. S.; Ganin, E. V.; Kotlyar, S. A. J. Inclusion Phenom. 1991, 11, 1.
38. 2 molecules, explains the R value obtained.
39. 2Zn (33 μL, 0.32 mmol) under argon. The resulting mixture was stirred at room temperature until the complete disappearance of the brown color and was recooled to -40 °C. Diiodomethane (26 μL, 0.32 mmol) was then slowly added, and the mixture was warmed to room temperature to produce unsuitable crystals. Subsequent addition of dichloromethane (400 μL) and warming the mixture to 35 °C dissolved the crystals. The solution was then cooled to 25 °C, and large crystals were formed in less than 15 min upon standing at that temperature.
40. The aggregation state will obviously depend on the nature of the solvent. For a review of the various proposals, see ref 2a.
41. Solutions of both complexes were effective cyclopropanating reagents. This is a consequence of the dynamic equilibrium between the complexed and uncomplexed forms of the reagent. Accordingly, the NMR spectra of these solutions indicate the presence of several species in solution.