The superiority of properly prepared lithium 1-N,N-dimethylaminonaphthalenide (LDMAN) over other aromatic radical-anions for the generation of organolithiums by reductive lithiation

Tetrahedron Letters

Volumn 51, Issue 1, 2010, Pages 174-176

  Ivanov, Roman ^a   Marek, Ilan ^b   Cohen, Theodore ^a  

^a UNIVERSITY OF PITTSBURGH   (United States)

^b TECHNION ISRAEL INSTITUTE OF TECHNOLOGY   (Israel)

Author keywords

[No Author keywords available]

Indexed keywords

AROMATIC COMPOUND; LITHIUM 1 N,N DIMETHYLAMINONAPHTHALENIDE; LITHIUM DERIVATIVE; ORGANOLITHIUM COMPOUND; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; COLUMN CHROMATOGRAPHY; LITHIATION; TEMPERATURE;

EID: 70649083233     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2009.10.121     Document Type: Article

References (62)

1. Screttas C.G., and Micha-Screttas M. J. Org. Chem. 43 (1978) 1064-1071
2. Cohen T., Daniewski W.M., and Weisenfeld R.B. Tetrahedron Lett. 19 (1978) 4665-4668
3. Yang A., Butela H., Deng K., Doubleday M.D., and Cohen T. Tetrahedron 62 (2006) 6526-6535 and citations therein
4. Cohen T., and Matz J.R. Synth. Commun. 10 (1980) 311-317
5. Freeman P.K., and Hutchinson L.L. J. Org. Chem. 45 (1980) 1924-1930
6. Cohen T., Kreethadumrongdat T., Liu X., and Kulkarni V. J. Am. Chem. Soc. 123 (2001) 3478-3483
7. In the earliest reports of the reductive lithiation of phenyl thioethers, there were several examples in which a sub-stoichiometric quantity of naphthalene was used along with a stoichiometric quantity of lithium metal: see Ref. 1a and (a) Screttas, C. G.; Micha-Screttas, M. J. Org. Chem. 1979, 44, 713-719. More recently, Yus's group has extensively utilized a form of the catalytic method in which a large excess of lithium is used along with a catalytic amount of the aromatic, usually naphthalene or p,p′-di-tert-butylbiphenyl: (b) Yus, M., In The Chemistry of Organolithium Compounds, Rappoport, Z. Marek, I., Ed.; Wiley: Chichester, 2004; Part 2, Chapter 11; (c) Ramón, D. J.; Yus, M. Eur. J. Org. Chem. 2000, 225-237.
8. Deng K., Bensari-Bouguerra A., Whetstone J., and Cohen T. J. Org. Chem. 71 (2006) 2360-2372
9. Deng K., Bensari A., and Cohen T. J. Am. Chem. Soc. 124 (2002) 12106-12107
10. Cheng D., Zhu S., Yu Z., and Cohen T. J. Am. Chem. Soc. 123 (2001) 30-34
11. Chen F., Mudryk B., and Cohen T. Tetrahedron 55 (1999) 3291-3304
12. Kulkarni V., and Cohen T. Tetrahedron 53 (1997) 12089-12100
13. Shook C.A., Romberger M.L., Jung S.-H., Xiao M., Sherbine J.P., Zhang B., Lin F.-T., and Cohen T. J. Am. Chem. Soc. 115 (1993) 10754-10773
14. Mudryk B., and Cohen T. J. Am. Chem. Soc. 115 (1993) 3855-3865
15. Cabral J.A., Cohen T., Doubleday W.W., Duchelle E.F., Fraenkel G., Guo B.-S., and Yü S.H. J. Org. Chem. 57 (1992) 3680-3684
16. McCullough D.W., Bhupathy M., Piccolino E., and Cohen T. Tetrahedron 47 (1991) 9727-9736
17. Cohen T., Jung S.-H., Romberger M.L., and McCullough D.W. Tetrahedron Lett. 29 (1988) 25-26
18. Guo B.-S., Doubleday W., and Cohen T. J. Am. Chem. Soc. 109 (1987) 4710-4711
19. Cohen T., and Guo B.-S. Tetrahedron 42 (1986) 2803-2808
20. Cohen T., Sherbine J.P., Mendelson S.A., and Myers M. Tetrahedron Lett. 26 (1985) 2965-2968
21. Cohen T., Sherbine J.P., Matz J.R., Hutchins R.R., McHenry B.M., and Willey P.R. J. Am. Chem. Soc. 106 (1984) 3245-3252
22. Cohen T., and Lin M.-T. J. Am. Chem. Soc. 106 (1984) 1130-1131
23. Cohen T., Bhupathy M., and Matz J.R. J. Am. Chem. Soc. 105 (1983) 520-525
24. Cohen T., Ouellette D., Senaratne K.P.A., and Yu L.-C. Tetrahedron Lett. 22 (1981) 3377-3380
25. Cohen T., and Matz J.R. J. Am. Chem. Soc. 102 (1980) 6900-6902
26. Chen F., Mudryk B., and Cohen T. Tetrahedron 50 (1994) 12793-12810
27. Streiff S., Ribeiro N., and Desaubry L. J. Org. Chem. 69 (2004) 7592-7598
28. Giannini A., Coquerel Y., Greene A.E., and Deprés J.P. Tetrahedron Lett. 45 (2004) 6749-6751
29. Tsai T.Y., Shia K.-S., and Liu H.-J. Synlett (2003) 97-101
30. Perales J.B., Makino N.F., and Van Vranken D.L. J. Org. Chem. 67 (2002) 6711-6717
31. Shimizu M., Hiyama T., Matsubara T., and Yamabe T. J. Organomet. Chem. 611 (2000) 12-19
32. Fraenkel G., and Qiu F. J. Am. Chem. Soc. 122 (2000) 12806-12812
33. Nowak A., and Schaumann E. Synthesis (1998) 899-904
34. Manteca I., Etxarri B., Ardeo A., Arrasate S., Osante I., Sotomayor N., and Lete E. Tetrahedron 54 (1998) 12361-12378
35. Tamao K., and Kawachi A. Organometallics 14 (1995) 3108-3111
36. Block E., Guo C., Thiruvazhi M., and Toscano P.J. J. Am. Chem. Soc. 116 (1994) 9403-9404
37. Block E., Schwan A., and Dixon D.A. J. Am. Chem. Soc. 114 (1992) 3492-3499
38. Tanaka K., Minami K., Funaki I., and Suzuki H. Tetrahedron Lett. 31 (1990) 2727-2730
39. McDougal P.G., and Condon B.D. Tetrahedron Lett. 30 (1989) 789-790
40. Keys B.A., Eliel E.L., and Juaristi E. Israel J. Chem. 29 (1989) 171-186
41. Brown P.A., Bonnert R.V., Jenkins P.R., and Selim M.R. Tetrahedron Lett. 28 (1987) 693-696
42. Barluenga J., Fernández-Simón J.L., Concellón J.M., and Yus M. J. Chem. Soc., Chem. Commun. (1987) 915-916
43. Barluenga J., and Ager D.J. J. Chem. Soc., Perkin Trans. 1 (1986) 183-194
44. Yus M., Concellon J.M., Bernad P., and Alvarez F. J. Chem. Res. (S) (1985) 128-129
45. Lyle T.A., Mereyala H.B., Pascual A., and Frei B. Helv. Chim. Acta 67 (1984) 774-778
46. Barluenga J., Flórez J., and Yus M. J. Chem. Soc., Perkin Trans. 1 (1983) 3019-3026
47. Kuwajima I., and Takeda R. Tetrahedron Lett. 22 (1981) 2381-2384
48. Recent reviews:. Strohmann C., and Schildbach D. In: Rappoport Z., and Marek I. (Eds). The Chemistry of Organolithium Compounds (2004), John Wiley, New York Chapter 15
49. Clayden J. Organolithiums: Selectivity for Synthesis (2002), Pergamon, London Chapter 4
50. recent papers reporting the use of LDBB: Refs. 2, 7a and 8a and. Merten J., Hennig A., Schwab P., Frohlich R., Tokalov S.V., Gutzeit H.O., and Metz P. Eur. J. Org. Chem. (2006) 1144-1161
51. Chen W., Zhao X., Lu L., and Cohen T. Org. Lett. 8 (2006) 2087-2090
52. Morin M.D., and Rychnovsky S.D. Org. Lett. 7 (2005) 2051-2053
53. La Cruz T.E., and Rychnovsky S.D. Org. Lett. 7 (2005) 1873-1875
54. de Vicente J., Betzemeier B., and Rychnovsky S.D. Org. Lett. 7 (2005) 1853-1856
55. Cooksey J., Gunn A., Kocienski P.J., Kuhl A., Uppal S., Christopher J.A., and Bell R. Org. Biomol. Chem. 2 (2004) 1719-1731
56. Wang L., and Floreancig P.E. Org. Lett. 6 (2004) 569-572
57. In some cases this was due to the sensitivity of the product of electrophile capture to the acid that was used to remove the dimethylaminonaphthalene byproduct: Brockunier, L. L., MS Thesis, University of Pittsburgh, 1988, p 21. However, even when the product is not acid-sensitive, some preliminary trials had indicated that LDBB gave superior results.
58. Cohen T., Sherbine J.P., Hutchins R.R., and Lin M.T. Organomet. Synth. 3 (1986) 361-368
59. 3,11 However, occasional irreproducibility and poor yields (for one literature example, see: Paquette, L. A.; Horn, K. A.; Wells, G. J. Tetrahedron Lett. 1982, 23, 259-262) led to speculation that lower temperatures may lead to better results and starting in 1999, the temperature of -55 °C was generally aimed for during the generation of LDMAN, although careful temperature control was not generally sought; apparently the first example was the lower temperature to prepare LDMAN only for the synthesis of 24 in: Chen, F.; Mudryk, B.; Cohen, T. Tetrahedron 1999, 55, 3291-3304. However, most other groups that have reported the use of LDMAN are still using the original recipe.
60. There may be automatic temperature controllers that can maintain the required narrow range, but we are unaware of any at this time.
61. General procedure for the reductive lithiation with LDMAN; To a three-neck round bottomed flask, equipped with a magnetic stirrer, argon inlet and a rubber septum was added 40 mL of dry THF. The flask was cooled to -55 °C. Lithium ribbon was prepared by scraping the dark oxide coating off of the surface while it was immersed in fresh mineral oil. The shiny metal was dipped into dry hexane in order to remove the oil and then weighed (0.1852 g, 0.0268 mol) in a tared beaker containing mineral oil. The metal was sliced into small pieces while it was still immersed in mineral oil. The lithium pieces were dipped again in hexane prior to the addition to the flask. Then DMAN (4.9 mL, 0.030 mol) was added quickly via syringe at -55 °C. A green color appeared in less than two minutes and became deep green in less than 5 min. The reaction mixture was stirred for 5 h at -55 ± 3 °C, and the resulting LDMAN solution was suitable for reductive lithiation of 0.0127 mol of substrate.
62. Abou A., Foubelo R., and Yus M. Arkivoc v (2007) 191-201