Dehalogenative and deprotonative lithiation of pyridines: A second wind for trimethylsilylmethylithium (TMSCH2Li)

Current Organic Chemistry

Volumn 15, Issue 14, 2011, Pages 2329-2339

  Gros, Philippe C ^a   Fort, Yves ^a  

^a NANCY UNIVERSITÉ   (France)

Author keywords

Aggregates; Functionalisation; Lithiation; Nucleophilicity; Pyridine; Selectivity; Trimethylsilylmethyllithium

Indexed keywords

ALKYLATION; LITHIUM COMPOUNDS;

FUNCTIONALIZATIONS; HALOGEN-METAL EXCHANGE; ITS APPLICATIONS; LITHIATION; METHYLENATION; NEW APPLICATIONS; NUCLEOPHILIC REAGENT; NUCLEOPHILICITIES; SELECTIVITY; TRIMETHYLSILYLMETHYLLITHIUM;

PYRIDINE;

EID: 79959969165     PISSN: 13852728     EISSN: None     Source Type: Journal    
DOI: 10.2174/138527211796150624     Document Type: Review

References (62)

1. Gros, P.; Fort, Y.; Queguiner, G.; Caubère, P. Aggregative activation and heterocyclic chemistry III. Unusual regioselective lithiation of 2-alkoxypyridines. Tetrahedron Lett. 1995, 36, 4791-4794.
2. Gros, P.; Fort, Y.; Caubère, P. J. Aggregative activation in heterocyclic chemistry. Part 4. Metallation of 2-methoxypyridine: unusual behaviour of the new unimetal superbase BuLi-Me2N(CH2)2OLi (BuLi-LiDMAE).Chem. Soc., Perkin Trans. 1 1997, 3071-3080.
3. Gros, P. C.; Fort, Y. nBuLi/Lithium Aminoalkoxide Aggregates: New and Promising Lithiating Agents for Pyridine Derivatives. Eur. J. Org. Chem. 2002, 2002, 3375-3383.
4. [Gros, P. C.; Fort, Y. Combinations of Alkyllithiums and Lithium Aminoalkoxides for Generation of Functional Pyridine Organometallics and Derivatives. Eur. J. Org. Chem. 2009, 4199-4209.
5. Khartabil, H. K.; Gros, P. C.; Fort, Y.; Ruiz-Lopez, M. F. Metalation of Pyridines with nBuLi-Li-Aminoalkoxide Mixed Aggregates: The Origin of Chemoselectivity. J. Am. Chem. Soc., 2010, 132, 2410-2416.
6. Sommer, L. H.; Mitch, F. A.; Goldberg, G. M. Synthesis and properties of compounds with a framework of alternate silicon and carbon atoms. J. Am. Chem. Soc. 1949, 71, 2746-2750.
7. Connolly, J. W.; Urry, G. Crystalline lithiomethyl trimethylsilane and some of its properties. Inorganic Chemistry 1963, 2, 645-646.
8. [T.-H. Alkene synthesis via.beta.-functionalized organosilicon compounds. Acc. Chem. Res. 1977, 10 (12), pp. 442-448.
9. Colvin, E. W. Silicon in organic synthesis. Chem. Soc. Rev. 1978, 7, 15-64.
10. [10] Magnus, P. D.; Sarkar, T.; Djuric, S. In Comprehensive Organometallic Chemistry; Wilkinson, G. S., F. G. A.; Abel, E. W., Ed.; Pergamon: Oxford: 1982; Vol. 7, p 515.
11. D. J. The Peterson olefination reaction. Org. React. 1990, 38, 1-223.
12. Ruden, R. A.; Gaffney, B. L. Trimethylsilylmethyl Ketones in Synthesis A Regiospecific Synthesis of b.beta, b.gamma-Unsaturated Esters, Amides and Nitriles. Synth. Commun. 1975, 15-19.
13. Wagner, J.; Vogel, P. Total, asymmetric synthesis of hexoses and azasugars branched at C(5). Tetrahedron 1991, 47, 9641-9658.
14. Mitchell, R. H.; Zhang, R.; Berg, D. J.; Twamley, B.; Williams, R. V. Measuring aromaticity with the dimethyldihydropyrene ring current probe. experimental and computational studies of the fulvenes and the strongly antiaromatic cyclopentadienone reveal large mills-nixon-type Bond localization effects. synthesis of fulvene-fused dihydropyrenes. J. Am. Chem. Soc. 2009, 131, 189-199.
15. Wang, B.; Wang, D.; Cui, D.; Gao, W.; Tang, T.; Chen, X.; Jing, X. Synthesis of the first rare earth metal bis(alkyl)s bearing an indenyl functionalized N-heterocyclic carbene. Organometallics 2007, 26, 3167-3172.
16. Tecle, B.; Maqsudur Rahman, A. F. M.; Oliver, J. P. X-ray crystal structure of trimethylsilylmethyllithium. J. Organomet. Chem. 1986, 317, 267-275.
17. Tanja, T.; Holger, O.; Dietmar, S. Deaggregation of Trimethylsilylmethyllithium. Eur. J. Inorg. Chem. 2008, 2008, 3765-3768.
18. [Fraser, R. R.; Baignee, A.; Bresse, M.; Hata, K. Lithium dialkylamides. 13C parameters and slow proton transfer. Tetrahedron Lett. 1982, 23, 4195-4198.
19. Marsais, F.; Queguiner, G. Review on the metallation of π -deficient heteroaromatic compounds. Regioselective ortho-lithiation of 3-fluoropyridine: Directing effects and application to synthesis of 2,3- or 3,4-disubstituted pyridines. Tetrahedron 1983, 39, 2009-2021.
20. Hosomi, A.; Ando, M.; Sakurai, H. Chemistry of organo-silicon compounds. 198. A novel and convenient regio-controlled synthesis of alpha-halogen-substituted allylsilanes - stereoselective synthesis of z-alkenyl halides. Chem. Lett.1984, 13, 1385-1388.
21. Comins, D. L.; LaMunyon, D. H. Ortho lithiation of 2-, 3-, and 4-methoxypyridines. Tetrahedron Lett. 1988, 29, 773-776.
22. Galiano-Roth, A. S.; Kim, Y. J.; Gilchrist, J. H.; Harrison, A. T.; Fuller, D. J.; Collum, D. B. Lithium diisopropylamide mixed aggregates: structures and consequences on the stereochemistry of ketone enolate formation. J. Am. Chem. Soc. 1991, 113, 5053-5055.
23. [Romesberg, F. E.; Collum, D. B. Determination of structures of solvated lithium dialkylamides by semiempirical (MNDO) methods. Comparison of theory and experiment. J. Am. Chem. Soc. 1992, 114, 2112-2121.
24. Olofson, R. A.; Dougherty, C. M. Lithium 2,2,6,6-tetramethylpiperidide and related, strong, proton-specific bases. Evaluation in synthesis. J. Am. Chem. Soc. 1973, 95, 582-584.
25. Taylor, S. L.; Lee, D. Y.; Martin, J. C. Direct, regiospecific 2-lithiation of pyridines and pyridine 1-oxides with in situ electrophilic trapping. J. Org. Chem. 1983, 48, 4156-4158.
26. Fraser, R. R.; Bresse, M.; Mansour, T. S. pKa Measurements in tetrahydrofuran. Chem. Commun. 1983, 620-621.
27. Hall, P. L.; Gilchrist, J. H.; Collum, D. B. Effects of lithium salts on the stereochemistry of ketone enolization by lithium 2,2,6,6-tetramethylpiperidide (LiTMP). A convenient method for highly E-selective enolate formation. J. Am. Chem. Soc. 1991, 113, 9571-9574.
28. Plé, N.; Turck, A.; Martin, P.; Barbey, S.; Queguiner, G. Metelation of diazines VIII metalation of 4-chloropyrimidine derivatives new synthesis of trimethoprim. Tetrahedron Lett. 1993, 34, 1605-1608.
29. Trécourt, F.; Marsais, F.; Güngör, T.; Quéguiner, G. Improved synthesis of 2,3-disubstituted pyridines by metallation of 2-chloropyridine: a convenient route to fused polyheterocycles. J. Chem. Soc., Perkin Trans. 1 1990, 2409.
30. Trecourt, F.; Mallet, M.; Marsais, F.; Queguiner, G. Catalyzed metalation applied to 2-methoxypyridine. J. Org. Chem. 1988, 53, 1367-1371.
31. [Woltermann, C. J.; Sutton, D. E. FMC Corporation, Using alkylmetal reagents for directed metalation of azaaromatics, PCT Int.Appl., WO 2004092125, 2004 (Chem. Abstr., 141, 366136).
32. Thomas, E. W. Synthesis of indolizinones and a pyridoazepinone: a new method for the annulation of pyridinones. J. Org. Chem. 1986, 51, 2184-2191.
33. Comins, D. L.; LaMunyon, D. H. Ortho lithiation of 2-, 3-, and 4- methoxypyridines. Tetrahedron Lett. 1988 29, 773-776.
34. Khartabil, H. K.; Gros, P. C.; Fort, Y.; Ruiz-Lopez, M. F. A Theoretical Study on nBuLi/Lithium Aminoalkoxide Aggregation in Hexane and THF. J. Org. Chem. 2008, 73, 9393-9402.
35. P.C. Gros, internal report 1998.
36. Choppin, S.; Gros, P.; Fort, Y. Unusual C-6 Lithiation of 2-Chloropyridine- Mediated by BuLi-Me2N(CH2)2OLi. New Access to 6-Functional-2- chloropyridines and Chloro-bis-heterocycles. Org. Lett. 2000, 2, 803-805.
37. Doudouh, A.; Gros, P. C.; Fort, Y.; Woltermann, C. TMSCH2Li-LiDMAE: a new nonnucleophilic reagent for C-2 lithiation of halopyridines. Tetrahedron 2006, 62, 6166-6171.
38. [Marsais, F.; Granger, P.; Quéguiner, G. Synthesis and structural study of 2,5- dihydropyridines. Competitive metalation of 2-fluoropyridine. J. Org. Chem. 1981, 46, 4494-4497.
39. Rodriguez, A.; Gros, P.; Fort, Y. First one-pot chemo-, regio- and enantioselective functionalisation of pyridine compounds mediated by BuLi-(S)-(-)- N-methyl-2-pyrrolidine methoxide. Tetrahedron: Asymmetry 2001, 12, 2631-2635.
40. Scriven, F.V. 4-Dialkylaminopyridines: super acylation and alkylation catalysts. Chem. Soc. Rev. 1983, 12, 129-161.
41. Ragnarsson, U.; Grehn, L. Novel Amine Chemistry Based on DMAPCatalyzed Acylation. Acc. Chem. Res. 1998, 31, 494-501.
42. Vedejs, E.; Chen, X. Kinetic Resolution of Secondary Alcohols. Enantioselective Acylation Mediated by a Chiral (Dimethylamino)pyridine Derivative. J. Am. Chem. Soc. 1996, 118, 1809-1810.
43. Spivey, A.; Maddaford, A.; Fekner, T.; Redgrave, A. J.; Frampton, C. S. Synthesis of C2-symmetric analogues of 4-(pyrrolidino)pyridine: new chiral nucleophilic catalysts. J. Chem. Soc., Perkin Trans. 1 2000, 3460-3468.
44. Cuperly, D.; Gros, P.; Fort, Y. First Direct C-2-Lithiation of 4-DMAP. Convenient Access to Reactive Functional Derivatives and Ligands. J. Org. Chem. 2002, 67, 238-241.
45. Martineau, D.; Beley, M.; Gros, P. C. Pyrrolidine-Containing Polypyridines: New Ligands for Improved Visible Light Absorption by Ruthenium Complexes. J. Org. Chem. 2006, 71, 566-571.
46. Glad, D., Master Research Report, 2006
47. Kessar, S.; Singh, P. Lewis Acid Complexation of Tertiary Amines and Related Compounds: A Strategy for α-Deprotonation and Stereocontrol. Chem. Rev. 1997, 97, 721-738.
48. Gros, P. C.; Doudouh, A.; Woltermann, C. First C-3 lithiation of DMAP: a new entry into chemical tuning of acylation catalysts. Chem. Commun. 2006, 2673-2674.
49. Gros, P. C.; Doudouh, A.; Woltermann, C. Concomitant morpholine ring contraction and pyridine lithiation in 4-morpholinopyridine: straightforward access to N-pyridyl oxazolidines. Tetrahedron Lett. 2008, 49, 4717-4719.
50. Breining, S. R. Recent Developments in the Synthesis of Nicotinic Acetylcholine Receptor Ligands. Curr. Top. Med. Chem. 2004, 4, 609-629.
51. Comins, D. L.; King, L. S.; Smith, E. D.; Février, F. C. Synthesis of C-4 Substituted Nicotine Derivatives via an N-Acylpyridinium Salt of (S)- Nicotine. Org. Lett. 2005, 7, 5059-5062.
52. Fevrier, F. C.; Smith, E. D.; Comins, D. L. Regioselective C-2 and C-6 Substitution of (S)-Nicotine and Nicotine Derivatives. Org. Lett. 2005, 7, 5457-5460.
53. Comins, D. L.; Smith, E. D. A six-step synthesis of (S)-5-ethenyl-3-(1- methyl-2-pyrrolidinyl)pyridine (SIB-1508Y) from (S)-nicotine. Tetrahedron Lett. 2006, 47, 1449.
54. Gros, P. C.; Doudouh, A.; Woltermann, C. TMSCH2Li-induced regioselective lithiation of (S)-nicotine. Org. 2006, 4, 4331-4335.
55. Doudouh, A.; Woltermann, C.; Gros, P. C. TMSCH2Li and TMSCH2Li-LiDMAE: Efficient Reagents for Noncryogenic Halogen -Lithium Exchange in Bromopyridines. J. Org. Chem. 2007, 72, 4978-4980.
56. Parham, W. E.; Piccirilli, R. M. Selective halogen-lithium exchange in 2,5- dibromobenzenes and 2,5-dibromopyridine. J. Org. Chem. 1977, 42, 257-260.
57. Bolm, C.; Ewald, M.; Felder, M.; Schlingloff, G. Enantioselective Synthesis of Optically Active Pyridine Derivatives and C2-Symmetric 2,2??-Bipyridines. Chem. Ber. 1992, 125, 1169-1190.
58. Romero-Salguero, F. J.; Lehn, J.-M. Synthesis of multitopic bidentate ligands based on alternating pyridine and pyridazine rings. Tetrahedron Lett. 1999, 40, 859-862.
59. Wang, X.; Rabbat, P.; O'Shea, P.; Tillyer, R.; Grabowski, E. J. J.; Reider, P. J. Selective monolithiation of 2,5-dibromopyridine with butyllithium. Tetrahedron Lett. 2000, 41, 4335-4338.
60. Mallet, M.; Queguiner, G. Nouvelles réactions d'halogenopyridines avec le n-butyllithium. proposition d'un mécanisme par métallation et migration du brome. Tetrahedron 1979, 35, 1625-1631.
61. Mallet, M.; Quéguiner, G. Action du n-butyllithium sur les bromo-3 halogeno- 2 pyridines fluoree, chloree et bromee. Principe et etude d'une possibilite reactionnelle nouvelle: l'homotransmetallation. Tetrahedron 1985, 41, 3433-3440.
62. Gros, P. C.; Elaachbouni, F. Bromine-lithium exchange under non-cryogenic conditions: TMSCH2Li-LiDMAE promoted C-2 lithiation of 2,3- dibromopyridine. Chem. Commun. 2008, 4813-4815.