Electrophile-promoted carbon - Sulfur bond cleavage in η2-thiophene complexes of pentaammineosmium(II)

Journal of the American Chemical Society

Volumn 119, Issue 38, 1997, Pages 8843-8851

  Spera, Michael L ^a   Harman, W Dean ^a  

^a UNIVERSITY OF VIRGINIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ORGANOMETALLIC COMPOUND; THIOPHENE DERIVATIVE;

ALKYLATION; ARTICLE; CHEMICAL BOND; CHEMICAL MODIFICATION; DRUG SYNTHESIS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030861557     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja970941k     Document Type: Article

References (56)

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2. For reviews of transition metal thiophene complexes, see: (a) Angelici, R. J. Coord. Chem. Rev. 1990, 105, 61 and references therein. (b) Rauchfuss, T. B. Prog. Inorg. Chem. 1991, 39, 259.
3. For recent examples of C-S insertion reactions, see: (a) Myers, A. W.; Jones, W. D. Organametallics 1996, 15, 2905. (b) Chen, J.; Young, V. G.; Angelici, R. J. Organometallics 1996, 15, 2727. (c) Chen, J.; Daniels, L. M.; Angelici, R. J. Organometallics 1996, 15, 1223. (d) Bianchini, C.; Meli, A. J. Chem. Soc., Dalton Trans. 1996, 801. (e) Myers, A. W.; Jones, W. D.; McClements, S. M. J. Am. Chem. Soc. 1995, 117, 11704. (f) Bianchini, C.; Frediani, P.; Herrera, V.; Jimenez, M. V.; Meli, A.; Rincon, L.; Sanchez-Delgado, R.; Vizza, F. J. Am. Chem. Soc. 1995, 117, 4333. (g) Bianchini, C.; Jimenez, M. V.; Meli, A.; Vizza, F. Organometallics 1995, 14, 4858.
4. For recent examples of C-S insertion reactions, see: (a) Myers, A. W.; Jones, W. D. Organametallics 1996, 15, 2905. (b) Chen, J.; Young, V. G.; Angelici, R. J. Organometallics 1996, 15, 2727. (c) Chen, J.; Daniels, L. M.; Angelici, R. J. Organometallics 1996, 15, 1223. (d) Bianchini, C.; Meli, A. J. Chem. Soc., Dalton Trans. 1996, 801. (e) Myers, A. W.; Jones, W. D.; McClements, S. M. J. Am. Chem. Soc. 1995, 117, 11704. (f) Bianchini, C.; Frediani, P.; Herrera, V.; Jimenez, M. V.; Meli, A.; Rincon, L.; Sanchez-Delgado, R.; Vizza, F. J. Am. Chem. Soc. 1995, 117, 4333. (g) Bianchini, C.; Jimenez, M. V.; Meli, A.; Vizza, F. Organometallics 1995, 14, 4858.
5. For recent examples of C-S insertion reactions, see: (a) Myers, A. W.; Jones, W. D. Organametallics 1996, 15, 2905. (b) Chen, J.; Young, V. G.; Angelici, R. J. Organometallics 1996, 15, 2727. (c) Chen, J.; Daniels, L. M.; Angelici, R. J. Organometallics 1996, 15, 1223. (d) Bianchini, C.; Meli, A. J. Chem. Soc., Dalton Trans. 1996, 801. (e) Myers, A. W.; Jones, W. D.; McClements, S. M. J. Am. Chem. Soc. 1995, 117, 11704. (f) Bianchini, C.; Frediani, P.; Herrera, V.; Jimenez, M. V.; Meli, A.; Rincon, L.; Sanchez-Delgado, R.; Vizza, F. J. Am. Chem. Soc. 1995, 117, 4333. (g) Bianchini, C.; Jimenez, M. V.; Meli, A.; Vizza, F. Organometallics 1995, 14, 4858.
6. For recent examples of C-S insertion reactions, see: (a) Myers, A. W.; Jones, W. D. Organametallics 1996, 15, 2905. (b) Chen, J.; Young, V. G.; Angelici, R. J. Organometallics 1996, 15, 2727. (c) Chen, J.; Daniels, L. M.; Angelici, R. J. Organometallics 1996, 15, 1223. (d) Bianchini, C.; Meli, A. J. Chem. Soc., Dalton Trans. 1996, 801. (e) Myers, A. W.; Jones, W. D.; McClements, S. M. J. Am. Chem. Soc. 1995, 117, 11704. (f) Bianchini, C.; Frediani, P.; Herrera, V.; Jimenez, M. V.; Meli, A.; Rincon, L.; Sanchez-Delgado, R.; Vizza, F. J. Am. Chem. Soc. 1995, 117, 4333. (g) Bianchini, C.; Jimenez, M. V.; Meli, A.; Vizza, F. Organometallics 1995, 14, 4858.
7. For recent examples of C-S insertion reactions, see: (a) Myers, A. W.; Jones, W. D. Organametallics 1996, 15, 2905. (b) Chen, J.; Young, V. G.; Angelici, R. J. Organometallics 1996, 15, 2727. (c) Chen, J.; Daniels, L. M.; Angelici, R. J. Organometallics 1996, 15, 1223. (d) Bianchini, C.; Meli, A. J. Chem. Soc., Dalton Trans. 1996, 801. (e) Myers, A. W.; Jones, W. D.; McClements, S. M. J. Am. Chem. Soc. 1995, 117, 11704. (f) Bianchini, C.; Frediani, P.; Herrera, V.; Jimenez, M. V.; Meli, A.; Rincon, L.; Sanchez-Delgado, R.; Vizza, F. J. Am. Chem. Soc. 1995, 117, 4333. (g) Bianchini, C.; Jimenez, M. V.; Meli, A.; Vizza, F. Organometallics 1995, 14, 4858.
8. For recent examples of C-S insertion reactions, see: (a) Myers, A. W.; Jones, W. D. Organametallics 1996, 15, 2905. (b) Chen, J.; Young, V. G.; Angelici, R. J. Organometallics 1996, 15, 2727. (c) Chen, J.; Daniels, L. M.; Angelici, R. J. Organometallics 1996, 15, 1223. (d) Bianchini, C.; Meli, A. J. Chem. Soc., Dalton Trans. 1996, 801. (e) Myers, A. W.; Jones, W. D.; McClements, S. M. J. Am. Chem. Soc. 1995, 117, 11704. (f) Bianchini, C.; Frediani, P.; Herrera, V.; Jimenez, M. V.; Meli, A.; Rincon, L.; Sanchez-Delgado, R.; Vizza, F. J. Am. Chem. Soc. 1995, 117, 4333. (g) Bianchini, C.; Jimenez, M. V.; Meli, A.; Vizza, F. Organometallics 1995, 14, 4858.
9. For recent examples of C-S insertion reactions, see: (a) Myers, A. W.; Jones, W. D. Organametallics 1996, 15, 2905. (b) Chen, J.; Young, V. G.; Angelici, R. J. Organometallics 1996, 15, 2727. (c) Chen, J.; Daniels, L. M.; Angelici, R. J. Organometallics 1996, 15, 1223. (d) Bianchini, C.; Meli, A. J. Chem. Soc., Dalton Trans. 1996, 801. (e) Myers, A. W.; Jones, W. D.; McClements, S. M. J. Am. Chem. Soc. 1995, 117, 11704. (f) Bianchini, C.; Frediani, P.; Herrera, V.; Jimenez, M. V.; Meli, A.; Rincon, L.; Sanchez-Delgado, R.; Vizza, F. J. Am. Chem. Soc. 1995, 117, 4333. (g) Bianchini, C.; Jimenez, M. V.; Meli, A.; Vizza, F. Organometallics 1995, 14, 4858.
10. For examples of nucleophilic additions with or without C-S activation, see: (a) Krautscheid, H.; Feng, Q.; Rauchfuss, T. B. Organometallics 1993, 12, 3273. (b) Hachgenei, J. W.; Angelici, R. J. J. Organomet. Chem. 1988, 355, 359. (c) Hachgenei, J. W.; Angelici, R. J. Angew. Chem., Int. Ed. Engl. 1987, 26, 909. (d) Spies, G. H.; Angelici, R. J. Organometallics 1987, 6, 1897.
11. For examples of nucleophilic additions with or without C-S activation, see: (a) Krautscheid, H.; Feng, Q.; Rauchfuss, T. B. Organometallics 1993, 12, 3273. (b) Hachgenei, J. W.; Angelici, R. J. J. Organomet. Chem. 1988, 355, 359. (c) Hachgenei, J. W.; Angelici, R. J. Angew. Chem., Int. Ed. Engl. 1987, 26, 909. (d) Spies, G. H.; Angelici, R. J. Organometallics 1987, 6, 1897.
12. For examples of nucleophilic additions with or without C-S activation, see: (a) Krautscheid, H.; Feng, Q.; Rauchfuss, T. B. Organometallics 1993, 12, 3273. (b) Hachgenei, J. W.; Angelici, R. J. J. Organomet. Chem. 1988, 355, 359. (c) Hachgenei, J. W.; Angelici, R. J. Angew. Chem., Int. Ed. Engl. 1987, 26, 909. (d) Spies, G. H.; Angelici, R. J. Organometallics 1987, 6, 1897.
13. For examples of nucleophilic additions with or without C-S activation, see: (a) Krautscheid, H.; Feng, Q.; Rauchfuss, T. B. Organometallics 1993, 12, 3273. (b) Hachgenei, J. W.; Angelici, R. J. J. Organomet. Chem. 1988, 355, 359. (c) Hachgenei, J. W.; Angelici, R. J. Angew. Chem., Int. Ed. Engl. 1987, 26, 909. (d) Spies, G. H.; Angelici, R. J. Organometallics 1987, 6, 1897.
14. 2-thiophene in a triosmium cluster, see: Arce, A.; De Sanctis, Y. J. Organomet. Chem. 1986, 311, 371.
15. 2-thiophene in a triosmium cluster, see: Arce, A.; De Sanctis, Y. J. Organomet. Chem. 1986, 311, 371.
16. 2-thiophene in a triosmium cluster, see: Arce, A.; De Sanctis, Y. J. Organomet. Chem. 1986, 311, 371.
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19. (a) Luo, S.; Rauchfuss, T. B.; Gan, Z. J. Am. Chem. Soc. 1993, 115, 4943.
20. (b) Luo, S.; Rauchfuss, T. B.; Wilson, S. R. J. Am. Chem. Soc. 1992, 114, 8515.
21. (a) Other electrophiles that react at C(2) include acetals and Michael acceptors: Spera, M. L.; Harman, W. D. Manuscript in preparation.
22. 2-thiophene complexes, see: Spera, M. L.; Harman, W. D. Organometallics 1995, 14, 1559.
23. For the synthesis and characterization of some S-alkylthiophenium salts, see: Acheson, R. M.; Harrison, D. R. J. Chem. Soc. (C) 1970, 1764 and references therein.
24. 2-cyclopentadiene complex readily undergoes hydrolysis in wet acetonitrile or acetone to afford the formyl-substituted allyl complex. Spera, M. L.; Lopez, K. W.; Harman, W. D. Unpublished results.
25. 2-pyrrole complexes, see: Hodges, L. M.; Gonzales, J.; Myers, W. H.; Koontz, J. I.; Harman, W. D. J. Org. Chem. 1995, 60, 2125. For furan, see: (a) Chen, H.; Hodges, L. M.; Liu, R.; Stevens, W. C.; Sabat, M.; Harman, W. D. J. Am. Chem. Soc. 1994, 116, 5499. (b) Liu, R.; Chen, H.; Harman, W. D. Organometallics 1995, 14, 2861.
26. 2-pyrrole complexes, see: Hodges, L. M.; Gonzales, J.; Myers, W. H.; Koontz, J. I.; Harman, W. D. J. Org. Chem. 1995, 60, 2125. For furan, see: (a) Chen, H.; Hodges, L. M.; Liu, R.; Stevens, W. C.; Sabat, M.; Harman, W. D. J. Am. Chem. Soc. 1994, 116, 5499. (b) Liu, R.; Chen, H.; Harman, W. D. Organometallics 1995, 14, 2861.
27. 2-pyrrole complexes, see: Hodges, L. M.; Gonzales, J.; Myers, W. H.; Koontz, J. I.; Harman, W. D. J. Org. Chem. 1995, 60, 2125. For furan, see: (a) Chen, H.; Hodges, L. M.; Liu, R.; Stevens, W. C.; Sabat, M.; Harman, W. D. J. Am. Chem. Soc. 1994, 116, 5499. (b) Liu, R.; Chen, H.; Harman, W. D. Organometallics 1995, 14, 2861.
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29. Chen, H.; Harman, W. D. J. Am. Chem. Soc. 1996, 118, 5672.
30. 2-olefin and vinyl ether complexes of pentaammineosmium(II) vary from 6.0 to 10.2 Hz. Cis-coupling constants vary from 4.8 to 9.0 Hz.
31. This silyl ketene acetal undergoes facile nucleophilic addition to various pentaammineosmium(II) areneium complexes.
32. 2-naphthalene complex. Winemiller, M. D.; Harman, W. D. Unpublished results.
33. Mozingo, R. Org. Syn. 1941, 21, 15. For a review describing the synthetic applications of Raney Nickel, see: Pizey, J. S. Synthetic Reagents; Wiley: New York, 1974; Vol 2, pp 175-311.
34. Mozingo, R. Org. Syn. 1941, 21, 15. For a review describing the synthetic applications of Raney Nickel, see: Pizey, J. S. Synthetic Reagents; Wiley: New York, 1974; Vol 2, pp 175-311.
35. The Raney nickel was purchased as a 50% wt/wt slurry in water from Aldrich. The water was removed (in a glovebox under nitrogen!) by repeatedly washing with anhydrous methanol and drying under a stream of nitrogen. The material should be used immediately since its activity decreases rapidly when stored as a dry solid. The slurry is usually stable for ∼6 months. Unwanted portions of this highly pyrophoric material may be conveniently destroyed by refluxing in a large volume of acetone overnight followed by dilution with water.
36. 3CN, the metal migrates to the olefin.
37. DDQ is a two-electron oxidant whose potential is 0.71 V (NHE) for the first electron transfer. In theory, only 0.5 equiv of oxidant is required to oxidize Os(II) to Os(III), however, we have found that ∼1.0 equiv is required for many Os(II) oxidations.
38. Observation of this product indicates solvent substitution on Os(III) for the desired ligand.
39. The oxidation potential of many oxidants, particularly small cations, varies considerably with the coordinating ability of the solvent. For a review of the use of various redox reagents in organometallic chemistry, see: Connelly, N. G.; Geiger, W. E. Chem. Rev. 1996, 96, 877.
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42. For examples of activation of arenes and heterocycles toward electrophilic additions, see for phenol: Kopach, M. E.; Gonzalez, J.; Harman, W. D. J. Am. Chem. Soc. 1991, 56, 4321. For aniline, see: Kolis, S. P.; Gonzalez, J.; Bright, L. M.; Harman, W. D. Organometallics 1996, 15, 245. For activation of pyrrole and furan, see ref 10.
43. (a) Protonation is believed to occur initially at sulfur, followed by rearrangement of the metal and transfer of the proton to C(2). See ref 7b. (b) Both substitution and addition products are observed at either C(2) or C(3) depending on the electrophile and substitution pattern of the thiophene ring. Spera, M. L.; Harman., W. D. Preliminary results.
44. Chen, J.; Daniels, L. M.; Angelici, R. J. J. Am. Chem. Soc. 1990, 112, 199.
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46. Lee, S. S.; Lee, T. Y.; Choi, D. S.; Lee, J. S.; Chung, Y. K.; Lee, S. W.; Lah, M. S. Organometallics 1997, 16, 1749.
47. 2-selenophene complex has been Se-alkylated in our laboratories in high (>95%) yield and undergoes a similar C-Se bond cleavage in the presence of nucleophiles. Spera, M. L.; Harman, W. D. Unpublished results.
48. Mitchell, P. C. H. Catalysis (London) 1981, 4, 175.
49. (a) Lay, P. A.; Magnuson, R. H.; Taube, H. Inorg. Chem. 1989, 28, 3001.
50. (b) Lay, P. A.; Magnuson, R. H.; Taube, H. Inorg. Synth. 1986, 24, 269. For an improved detailed procedure for the synthesis of this reagent, see: Gonzalez, J. Ph. D. Dissertation, University of Virginia, May, 1995. This compound is currently available from Aldrich.
51. (b) Lay, P. A.; Magnuson, R. H.; Taube, H. Inorg. Synth. 1986, 24, 269. For an improved detailed procedure for the synthesis of this reagent, see: Gonzalez, J. Ph. D. Dissertation, University of Virginia, May, 1995. This compound is currently available from Aldrich.
52. 6 counteranion for triflate.
53. This operation is most easily carried out under dry nitrogen in a glovebox.
54. This compound has been previously reported. See Crow, W. D.; McNab, H. Aust. J. Chem. 1979, 32, 123.
55. This compound has been previously reported. See: (a) Everhardus, R. H.; Gräfing, R.; Brandsma, L. Synth. Commun. 1983, 623. (b) Crumbie, R. L.; Ridley, D. D. Aust. J. Chem. 1981, 34, 1017.
56. This compound has been previously reported. See: (a) Everhardus, R. H.; Gräfing, R.; Brandsma, L. Synth. Commun. 1983, 623. (b) Crumbie, R. L.; Ridley, D. D. Aust. J. Chem. 1981, 34, 1017.