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Reaction between benzyllithium and 2-ethylpyridine: chiral crystals of a 1-(2-pyridyl)ethyllithium complex versus formation of lithium 4-benzyl-2-ethyl-1,4-dihydropyridinide

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Abstract

The reaction between benzyllithium and prochiral 2-ethylpyridine in tetrahydrofuran has been studied. In the presence of N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDTA), it was found that 1-(2-pyridyl)ethyllithium was formed as a PMDTA complex. This complex is mononuclear, with lithium coordinated to the pyridyl nitrogen atom only; there are no short lithium–carbon distances and the structure approaches that of an enamide rather than a carbanion. The complex undergoes spontaneous resolution and forms chiral crystals with two molecules in the asymmetric unit; the two molecules have different configurations at the chirogenic pyridyl nitrogen atoms but share the same chiral conformation of the chelate ring systems. Reaction between benzyllithium and 2-ethylpyridine in tetrahydrofuran in the absence of PMDTA was found to give a high proportion of lithium 4-benzyl-2-ethyl-1,4-dihydropyridinide, and crystals of a dinuclear complex displaying tetrahydrofuran ligands and co-crystallised n-hexane molecules were isolated.

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References

  1. Lennartson A, Olsson S, Sundberg J, Håkansson M (2009) Angew Chem Int Ed 48:3137

    Article  CAS  Google Scholar 

  2. Lennartson A, Sundberg J, Wiklund T, Hilmersson G, Håkansson M (2010) Eur J Inorg Chem 3029

  3. Lennartson A, Hedström A, Håkansson M (2010) Organometallics 29:177

    Article  CAS  Google Scholar 

  4. Hoffmann RW, Ruehl T, Chemla F, Zahneisen T (1992) Liebigs Ann Chem 719

  5. Hoffmann RW, Ruehl T, Harbach J (1992) Liebigs Ann Chem 725

  6. Curtin DY, Koehl Jr WJ (1960) Chem Ind 262

  7. Letsinger RL (1950) J Am Chem Soc 72:4842

    Article  CAS  Google Scholar 

  8. Guijarro A, Rieke RD (2000) Angew Chem Int Ed 39:1475

    Article  CAS  Google Scholar 

  9. Jacques J, Collet A, Wilen SH (1984) Enantiomers racemates and resolutions. Wiley, New York

    Google Scholar 

  10. Flack HD (2003) Helv Chim Acta 86:905

    Article  CAS  Google Scholar 

  11. Wallentin C-J, Orentas E, Wärnmark K, Wendt OF (2009) Z Kristallogr 224:607

    Article  CAS  Google Scholar 

  12. Jacques J, Leclercq M, Brienne MJ (1981) Tetrahedron 37:1727

    Article  CAS  Google Scholar 

  13. Matsuura T, Koshima H (2005) J Photochem Photobiol C Photochem Rev 6:7

    Article  CAS  Google Scholar 

  14. Feringa BL, van Delden RA (1999) Angew Chem Int Ed 38:3419

    Article  CAS  Google Scholar 

  15. Mislow K (2003) Collect Czech Chem Commun 68:849

    Article  CAS  Google Scholar 

  16. Broaddus CD (1970) J Org Chem 35:10

    Article  CAS  Google Scholar 

  17. Ott H, Pieper U, Leusser D, Flierler U, Henn J, Stalke D (2009) Angew Chem Int Ed 48:2978

    Article  CAS  Google Scholar 

  18. Allen FH (2002) Acta Crystallogr B 58:380

    Article  Google Scholar 

  19. Papasergio RI, Raston CL, White AH (1983) J Chem Soc Chem Commun 1419

  20. Colagon D, Papasergio RI, Raston CL, White AH (1984) J Chem Soc Chem Commun 1708

  21. Hacker R, PvR Schleyer, Reber G, Mueller G, Brandsma L (1986) J Organomet Chem 316:C4

    Article  CAS  Google Scholar 

  22. Jones C, Kennard CHL, Raston CL, Smith G (1990) J Organomet Chem 396:C39

    Article  CAS  Google Scholar 

  23. Kabak M, Elmali A, Ozbey S, Atakol O, Kenar A (1996) Z Kristallogr 211:831

    Article  CAS  Google Scholar 

  24. Mostad A, Roemming C, Tressum L (1975) Acta Chem Scand B29:171

    Article  CAS  Google Scholar 

  25. Kuroda R, Honma T (2000) Chirality 12:269

    Article  CAS  Google Scholar 

  26. Kuroda R (2000) Circular dichroism. Wiley, New York

    Google Scholar 

  27. Lennartson A, Vestergren M, Håkansson M (2005) Chem Eur J 11:1757

    Article  CAS  Google Scholar 

  28. Lennartson A, Wiklund T, Håkansson M (2007) Cryst Eng Comm 9:856

    CAS  Google Scholar 

  29. Lennartson A, Håkansson M (2009) Acta Crystallogr C 65:m205

    Article  Google Scholar 

  30. Pettersen A, Lennartson A, Håkansson M (2009) Organometallics 28:3567

    Article  CAS  Google Scholar 

  31. Vestergren M, Eriksson J, Håkansson M (2003) Chem Eur J 9:4678

    Article  CAS  Google Scholar 

  32. Vestergren M, Johansson A, Lennartson A, Håkansson M (2004) Mendeleev Commun 258

  33. Lennartson A, Håkansson M (2009) Angew Chem Int Ed 48:5869

    Article  CAS  Google Scholar 

  34. Lennartson A, Håkansson M (2009) Cryst Eng Comm 11:1979

    CAS  Google Scholar 

  35. Kondepudi DK, Kaufman RJ, Singh N (1990) Science 250:975

    Article  CAS  Google Scholar 

  36. McBride JM, Carter RL (1991) Angew Chem Int Ed 30:293

    Article  Google Scholar 

  37. Viedma C (2005) Phys Rev Lett 94:065504/1

    Google Scholar 

  38. Nishio M (2004) Cryst Eng Comm 6:130

    CAS  Google Scholar 

  39. Nishio M, Umezawa Y, Honda K, Tsuboyama S, Suezawa H (2009) Cryst Eng Comm 11:1757

    CAS  Google Scholar 

  40. Gilman H, McNinch HA (1962) J Org Chem 27:1889

    Article  CAS  Google Scholar 

  41. Abramovitch RA, Poulton GA (1969) J Chem Soc B 901

  42. Hampe D, Guenther W, Goerls H, Anders E (2004) Eur J Org Chem 4357

  43. Anders E, Opitz A, Boese R (1992) Chem Ber 125:1267

    Article  CAS  Google Scholar 

  44. Clegg W, Dunbar L, Horsburgh L, Mulvey RE (1996) Angew Chem Int Ed 35:753

    Article  CAS  Google Scholar 

  45. Hage M, Ogle CA, Rathman L, Hubbard JL (1998) Main Group Met Chem 21:777

    Article  CAS  Google Scholar 

  46. Patterman SP, Karle IL, Stucky GD (1970) J Am Chem Soc 92:1150

    Article  CAS  Google Scholar 

  47. Håkansson M (1998) Inorg Synth 32:222

    Article  Google Scholar 

  48. Rigaku (1998–2001) CrystalClear 1.3. Rigaku, Tokyo, Japan

  49. Altomare A, Cascarano G, Giacovazzo C, Gualardi A (1993) J Appl Crystallogr 26:343

    Article  Google Scholar 

  50. Sheldrick GM (2008) Acta Crystallogr A 64:112

    Article  Google Scholar 

  51. Farrugia LJ (1997) J Appl Crystallogr 30:565

    Article  CAS  Google Scholar 

  52. Spek AL (2002) PLATON a multipurpose crystallographic tool. Utrecht University, Utrecht, The Netherlands

    Google Scholar 

  53. Spek AL (1990) Acta Crystallogr A 46:C34

    Google Scholar 

  54. Farrugia LJ (1999) J Appl Crystallogr 32:837

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Physics and Chemistry, University of Southern Denmark, Campusvej 55, 5230, Odense M, Denmark

    Tove Wiklund & Anders Lennartson

  2. Department of Chemistry, University of Gothenburg, 412 96, Gothenburg, Sweden

    Susanne Olsson

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  1. Tove Wiklund
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  2. Susanne Olsson
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  3. Anders Lennartson
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Correspondence to Anders Lennartson.

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Wiklund, T., Olsson, S. & Lennartson, A. Reaction between benzyllithium and 2-ethylpyridine: chiral crystals of a 1-(2-pyridyl)ethyllithium complex versus formation of lithium 4-benzyl-2-ethyl-1,4-dihydropyridinide. Monatsh Chem 142, 813–819 (2011). https://doi.org/10.1007/s00706-011-0519-1

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  • DOI: https://doi.org/10.1007/s00706-011-0519-1

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