Contribution to the study of the mechanism of directed remote-metalation. Evidence for the intermediacy of a geminal dimetallo dialkoxide C(OM) 2 (M = Li, K), first doubly charged director of ortho metalation

Organic Letters

Volumn 7, Issue 5, 2005, Pages 827-830

  Tilly, David ^a   Samanta, Subhendu S ^a,b   De, Asish ^b   Castanet, Anne Sophie ^a   Mortier, Jacques ^a  

^a UNIVERSITÉ DU MAINE   (France)

^b DEPARTMENT OF MATERIALS SCIENCE   (India)

Author keywords

[No Author keywords available]

Indexed keywords

CARBOXYLIC ACID DERIVATIVE; FLUORENE DERIVATIVE; KETONE DERIVATIVE; LITHIUM DERIVATIVE; POTASSIUM DERIVATIVE;

ACIDITY; ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; CYCLIZATION; METALLATION; REACTION ANALYSIS; SUBSTITUTION REACTION;

EID: 15044347053     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0474709     Document Type: Article

References (37)

1. (a) Gohier, F.; Castanet, A.-S.; Mortier, J. Org. Lett. 2003, 5, 1919.
2. (b) Gohier, F.; Mortier, J. J. Org. Chem. 2003, 68, 2030 and references therein.
3. Hartung, C. G.; Snieckus, V. Modern Arene Chemistry; Astruc, D., Ed.; Wiley-VCH: New York, 2002; p 330.
4. Tilly, T.; Samanta, S. S.; Faigl, F.; Mortier, J. Tetrahedron Lett. 2002, 43, 8347.
5. (a) Beak, P.; Meyers, A. I. Acc. Chem. Res. 1986, 19, 356.
6. (b) Whisler, M. N.; MacNeil, S.; Snieckus, V.; Beak, P. Angew. Chem, Int. Ed. 2004, 43, 2206.
7. For recent reviews on reaction of organolithium compounds with alkali metal alkoxides and reactions of superbases, see: (a) Lochmann, L. Eur. J. Inorg. Chem. 2000, 1115. (b) Schlosser, M. Eur. J. Org. Chem. 2001, 3975.
8. For recent reviews on reaction of organolithium compounds with alkali metal alkoxides and reactions of superbases, see: (a) Lochmann, L. Eur. J. Inorg. Chem. 2000, 1115. (b) Schlosser, M. Eur. J. Org. Chem. 2001, 3975.
9. Although it is generally admitted that LICKOR needs to be handled below -50°C because of the rapid decomposition of the solvent (usually THF), this result shows that it is not necessarily the case if the base reacts faster with the substrate than with the solvent.
10. 8 displays broad signals with poor resolution in the aromatic region that are probably due to the presence of aggregates that prevent a simple structural elucidation.
11. Dialkoxide 4 is not trappable by electrophiles: treatment of the species 4 with iodomethane or dimethyl sulfate gave the fluorenone 7 even when hydrolysis of the reaction mixture with water was omitted. The replacement of one atom of metal (M = Li or K) by an alkyl group gave an unstable salt C(OM)(OR) that lost alkoxide ion before a second substitution occurred to produce a ketal. See: (a) Bluhm, H. F.; Donn, H. V.; Zook, H. D. J. Am. Chem. Soc. 1955, 77, 4406. These results are consistent with the findings of the reaction of the diethyl amide corresponding to 1: (b) Fu, J.-m. Ph.D. Thesis, University of Waterloo, 1990.
12. Dialkoxide 4 is not trappable by electrophiles: treatment of the species 4 with iodomethane or dimethyl sulfate gave the fluorenone 7 even when hydrolysis of the reaction mixture with water was omitted. The replacement of one atom of metal (M = Li or K) by an alkyl group gave an unstable salt C(OM)(OR) that lost alkoxide ion before a second substitution occurred to produce a ketal. See: (a) Bluhm, H. F.; Donn, H. V.; Zook, H. D. J. Am. Chem. Soc. 1955, 77, 4406. These results are consistent with the findings of the reaction of the diethyl amide corresponding to 1: (b) Fu, J.-m. Ph.D. Thesis, University of Waterloo, 1990.
13. (a) Hodge, P.; Perry, G. M.; Yates, P. J. Chem. Soc., Perkin Trans. 1 1977, 680.
14. (b) Bluhn, H. F.; Donn, H. V.; Zook, H. D. J. Am. Chem. Soc. 1955, 77, 4406.
15. (a) Rawson, G.; Wynberg, H. Recl. Trav. Chim. Pays-Bas 1971, 90, 46.
16. (b) Gassman, P. G.; Lumb, J. T.; Zalar, F. V. J. Am. Chem. Soc. 1967, 89, 946.
17. (c) Davies, D. G.; Derenberg, M.; Hodge, P. J. Chem. Soc. C 1971, 455.
18. (a) Lochmann, L. Collect. Czech. Chem. Commun. 1987, 52, 2710.
19. (b) Schlosser, M.; Choi, J. H.; Takagishi, S. Tetrahedron 1990, 46, 5633.
20. (a) Bauer, W.; Lochmann, L. J. Am. Chem. Soc. 1992, 114, 7482.
21. (b) Kremer, T.; Harder, S.; Junge, M.; Schleyer, P. v. R. Organometallics 1996, 15, 585.
22. Filler, R.; Fiebig, A. E.; Pelister, M. Y. J. Org. Chem. 1980, 45, 1290.
23. Reaction of the isolated fluorenone 7 with LICKOR (3.5 equiv) in benzene at 60°C led to the 1,2-addition product 9-butyl-9H-fluoren-9-ol (15%).
24. Parham, W. E.; Sayed, Y. A. J. Org. Chem. 1974, 39, 2051.
25. Alo, B. I.; Familoni, O. B. J. Chem. Soc., Perkin Trans. 1 1990, 1611.
26. General Procedure. n-Butyllithium (4.5 mL, 7.8 mmol) was added to a suspension of potassium tert-butoxide (792 mg, 7.07 mmol) in benzene (10 mL) at ambient temperature. After the mixture was stirred for 5 min, LICKOR was transferred into a round flask containing 2-biphenyl carboxylic acid (1) (400 mg, 2.02 mmol) in benzene (5 mL). Stirring was maintained for 1 h at 60°C, and the temperature was allowed to cool to room temperature. n-Butyllithium (2.5 mL, 4.05 mmol) was added dropwise, and the mixture was stirred at 60°C for an additional 2 h. After the reaction mixture was warmed to room temperature gradually, the reaction was quenched with the electrophile (40.4 mmol) in benzene (6 mL). Standard workup provided the desired fluorenone, which was purified by chromatography on silica gel (cyclohexane/ethyl acetate 90:10).
27. (Trimethylsilyl)-9H-fluoren-9-one that is produced by trapping the intermediate with chlorotrimethylsilane is not stable under these conditions. The silyl group is presumably metalated. See inter alia: (a) Wang, G.; Snieckus, V. J. Org. Chem. 1992, 57, 424. (b) Brough, P. A.; Fisher, S.; Zhao, B.-P.; Thomas, R. C.; Snieckus, V. Tetrahedron Lett. 1996, 37, 2915. (c) Mohri, S.-I.; Stefinovic, M.; Snieckus, V. J. Org. Chem. 1997, 62, 7072 and references therein.
28. (Trimethylsilyl)-9H-fluoren-9-one that is produced by trapping the intermediate with chlorotrimethylsilane is not stable under these conditions. The silyl group is presumably metalated. See inter alia: (a) Wang, G.; Snieckus, V. J. Org. Chem. 1992, 57, 424. (b) Brough, P. A.; Fisher, S.; Zhao, B.-P.; Thomas, R. C.; Snieckus, V. Tetrahedron Lett. 1996, 37, 2915. (c) Mohri, S.-I.; Stefinovic, M.; Snieckus, V. J. Org. Chem. 1997, 62, 7072 and references therein.
29. (Trimethylsilyl)-9H-fluoren-9-one that is produced by trapping the intermediate with chlorotrimethylsilane is not stable under these conditions. The silyl group is presumably metalated. See inter alia: (a) Wang, G.; Snieckus, V. J. Org. Chem. 1992, 57, 424. (b) Brough, P. A.; Fisher, S.; Zhao, B.-P.; Thomas, R. C.; Snieckus, V. Tetrahedron Lett. 1996, 37, 2915. (c) Mohri, S.-I.; Stefinovic, M.; Snieckus, V. J. Org. Chem. 1997, 62, 7072 and references therein.
30. These include, inter alia, reactions of 2-, 3-, and 4-pyridylbenzoates: (a) Rebstock, A.-S.; Mongin, F.; Trécourt, F.; Quéguiner, G. Tetrahedron 2003, 59, 4973. 2-Biphenyl diethylamide: (b) Fu, J.-M.; Zhao, B.-P.; Sharp, M. J.; Snieckus, V. J. Org. Chem. 1991, 56, 1683. (c) Fu, J.-m.; Snieckus, V. Can. J. Chem. 2000, 78, 905. (d) Wang, W.; Snieckus, V. J. Org. Chem. 1992, 57, 424. 2-Aminobiphenyl: (e) Narasimhan, N. S.; Alurhar, R. H. Indian J. Chem. 1969, 7, 1280. (f) Narasimhan, N. S.; Chandrachood, P. S. Synthesis 1979, 589. (g) Narasimhan, N. S.; Chandrachood, P. S.; Shete, N. R. Tetrahedron 1981, 37, 825. 1-(2′-Carboxyphenyl)pyrrole: (h) Cartoon, M. E. K.; Cheeseman, G. W. H. J. Organomet. Chem. 1981, 2/2, 1.
31. These include, inter alia, reactions of 2-, 3-, and 4-pyridylbenzoates: (a) Rebstock, A.-S.; Mongin, F.; Trécourt, F.; Quéguiner, G. Tetrahedron 2003, 59, 4973. 2-Biphenyl diethylamide: (b) Fu, J.-M.; Zhao, B.-P.; Sharp, M. J.; Snieckus, V. J. Org. Chem. 1991, 56, 1683. (c) Fu, J.-m.; Snieckus, V. Can. J. Chem. 2000, 78, 905. (d) Wang, W.; Snieckus, V. J. Org. Chem. 1992, 57, 424. 2-Aminobiphenyl: (e) Narasimhan, N. S.; Alurhar, R. H. Indian J. Chem. 1969, 7, 1280. (f) Narasimhan, N. S.; Chandrachood, P. S. Synthesis 1979, 589. (g) Narasimhan, N. S.; Chandrachood, P. S.; Shete, N. R. Tetrahedron 1981, 37, 825. 1-(2′-Carboxyphenyl)pyrrole: (h) Cartoon, M. E. K.; Cheeseman, G. W. H. J. Organomet. Chem. 1981, 2/2, 1.
32. These include, inter alia, reactions of 2-, 3-, and 4-pyridylbenzoates: (a) Rebstock, A.-S.; Mongin, F.; Trécourt, F.; Quéguiner, G. Tetrahedron 2003, 59, 4973. 2-Biphenyl diethylamide: (b) Fu, J.-M.; Zhao, B.-P.; Sharp, M. J.; Snieckus, V. J. Org. Chem. 1991, 56, 1683. (c) Fu, J.-m.; Snieckus, V. Can. J. Chem. 2000, 78, 905. (d) Wang, W.; Snieckus, V. J. Org. Chem. 1992, 57, 424. 2-Aminobiphenyl: (e) Narasimhan, N. S.; Alurhar, R. H. Indian J. Chem. 1969, 7, 1280. (f) Narasimhan, N. S.; Chandrachood, P. S. Synthesis 1979, 589. (g) Narasimhan, N. S.; Chandrachood, P. S.; Shete, N. R. Tetrahedron 1981, 37, 825. 1-(2′-Carboxyphenyl)pyrrole: (h) Cartoon, M. E. K.; Cheeseman, G. W. H. J. Organomet. Chem. 1981, 2/2, 1.
33. These include, inter alia, reactions of 2-, 3-, and 4-pyridylbenzoates: (a) Rebstock, A.-S.; Mongin, F.; Trécourt, F.; Quéguiner, G. Tetrahedron 2003, 59, 4973. 2-Biphenyl diethylamide: (b) Fu, J.-M.; Zhao, B.-P.; Sharp, M. J.; Snieckus, V. J. Org. Chem. 1991, 56, 1683. (c) Fu, J.-m.; Snieckus, V. Can. J. Chem. 2000, 78, 905. (d) Wang, W.; Snieckus, V. J. Org. Chem. 1992, 57, 424. 2-Aminobiphenyl: (e) Narasimhan, N. S.; Alurhar, R. H. Indian J. Chem. 1969, 7, 1280. (f) Narasimhan, N. S.; Chandrachood, P. S. Synthesis 1979, 589. (g) Narasimhan, N. S.; Chandrachood, P. S.; Shete, N. R. Tetrahedron 1981, 37, 825. 1-(2′-Carboxyphenyl)pyrrole: (h) Cartoon, M. E. K.; Cheeseman, G. W. H. J. Organomet. Chem. 1981, 2/2, 1.
34. These include, inter alia, reactions of 2-, 3-, and 4-pyridylbenzoates: (a) Rebstock, A.-S.; Mongin, F.; Trécourt, F.; Quéguiner, G. Tetrahedron 2003, 59, 4973. 2-Biphenyl diethylamide: (b) Fu, J.-M.; Zhao, B.-P.; Sharp, M. J.; Snieckus, V. J. Org. Chem. 1991, 56, 1683. (c) Fu, J.-m.; Snieckus, V. Can. J. Chem. 2000, 78, 905. (d) Wang, W.; Snieckus, V. J. Org. Chem. 1992, 57, 424. 2-Aminobiphenyl: (e) Narasimhan, N. S.; Alurhar, R. H. Indian J. Chem. 1969, 7, 1280. (f) Narasimhan, N. S.; Chandrachood, P. S. Synthesis 1979, 589. (g) Narasimhan, N. S.; Chandrachood, P. S.; Shete, N. R. Tetrahedron 1981, 37, 825. 1-(2′-Carboxyphenyl)pyrrole: (h) Cartoon, M. E. K.; Cheeseman, G. W. H. J. Organomet. Chem. 1981, 2/2, 1.
35. These include, inter alia, reactions of 2-, 3-, and 4-pyridylbenzoates: (a) Rebstock, A.-S.; Mongin, F.; Trécourt, F.; Quéguiner, G. Tetrahedron 2003, 59, 4973. 2-Biphenyl diethylamide: (b) Fu, J.-M.; Zhao, B.-P.; Sharp, M. J.; Snieckus, V. J. Org. Chem. 1991, 56, 1683. (c) Fu, J.-m.; Snieckus, V. Can. J. Chem. 2000, 78, 905. (d) Wang, W.; Snieckus, V. J. Org. Chem. 1992, 57, 424. 2-Aminobiphenyl: (e) Narasimhan, N. S.; Alurhar, R. H. Indian J. Chem. 1969, 7, 1280. (f) Narasimhan, N. S.; Chandrachood, P. S. Synthesis 1979, 589. (g) Narasimhan, N. S.; Chandrachood, P. S.; Shete, N. R. Tetrahedron 1981, 37, 825. 1-(2′-Carboxyphenyl)pyrrole: (h) Cartoon, M. E. K.; Cheeseman, G. W. H. J. Organomet. Chem. 1981, 2/2, 1.
36. These include, inter alia, reactions of 2-, 3-, and 4-pyridylbenzoates: (a) Rebstock, A.-S.; Mongin, F.; Trécourt, F.; Quéguiner, G. Tetrahedron 2003, 59, 4973. 2-Biphenyl diethylamide: (b) Fu, J.-M.; Zhao, B.-P.; Sharp, M. J.; Snieckus, V. J. Org. Chem. 1991, 56, 1683. (c) Fu, J.-m.; Snieckus, V. Can. J. Chem. 2000, 78, 905. (d) Wang, W.; Snieckus, V. J. Org. Chem. 1992, 57, 424. 2-Aminobiphenyl: (e) Narasimhan, N. S.; Alurhar, R. H. Indian J. Chem. 1969, 7, 1280. (f) Narasimhan, N. S.; Chandrachood, P. S. Synthesis 1979, 589. (g) Narasimhan, N. S.; Chandrachood, P. S.; Shete, N. R. Tetrahedron 1981, 37, 825. 1-(2′-Carboxyphenyl)pyrrole: (h) Cartoon, M. E. K.; Cheeseman, G. W. H. J. Organomet. Chem. 1981, 2/2, 1.
37. These include, inter alia, reactions of 2-, 3-, and 4-pyridylbenzoates: (a) Rebstock, A.-S.; Mongin, F.; Trécourt, F.; Quéguiner, G. Tetrahedron 2003, 59, 4973. 2-Biphenyl diethylamide: (b) Fu, J.-M.; Zhao, B.-P.; Sharp, M. J.; Snieckus, V. J. Org. Chem. 1991, 56, 1683. (c) Fu, J.-m.; Snieckus, V. Can. J. Chem. 2000, 78, 905. (d) Wang, W.; Snieckus, V. J. Org. Chem. 1992, 57, 424. 2-Aminobiphenyl: (e) Narasimhan, N. S.; Alurhar, R. H. Indian J. Chem. 1969, 7, 1280. (f) Narasimhan, N. S.; Chandrachood, P. S. Synthesis 1979, 589. (g) Narasimhan, N. S.; Chandrachood, P. S.; Shete, N. R. Tetrahedron 1981, 37, 825. 1-(2′-Carboxyphenyl)pyrrole: (h) Cartoon, M. E. K.; Cheeseman, G. W. H. J. Organomet. Chem. 1981, 2/2, 1.