Structural Chemistry

, Volume 19, Issue 5, pp 785–792 | Cite as

A computational study of the effect of C-lithiation on the NMR properties (chemical shifts and coupling constants) of aziridines

  • Vito Capriati
  • Saverio Florio
  • Renzo Luisi
  • Biagia Musio
  • Ibon Alkorta
  • Fernando Blanco
  • José Elguero
Original Research

Abstract

A DFT (B3LYP/6-311++G(d,p) study of a series of N-H, N-methyl and N-propyl aziridines and their C-lithium derivatives has been carried out in order to explore their configurational as well as their NMR properties (1H and 13C). The results agree fairly well with experimental observations [Org Lett 9:1263, 2007 and J Org Chem 73, 2008 (73:3197)] and reveal the existence of lithium-N(lone pair) and lithium C(aromatic) interactions.

Keywords

Aziridines Lithium derivatives B3LYP GIAO 

Supplementary material

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References

  1. 1.
    Luisi R, Capriati V, Florio S, Musio B (2007) Org Lett 9:1263. doi:10.1021/ol0700714 CrossRefGoogle Scholar
  2. 2.
    Capriati V, Florio S, Luisi R, Mazzanti A, Musio B (2008) J Org Chem 73:3197. doi:10.1021/jo800069k CrossRefGoogle Scholar
  3. 3.
    Johnels D, Andersson A, Boman A, Edlund U (1996) Magn Reson Chem 34:908CrossRefGoogle Scholar
  4. 4.
    (a) Becke AD (1993) J Chem Phys 98:5648. doi:10.1063/1.464913; (b) Lee C, Yang W, Parr RG (1988) Phys Rev A 37:785. doi:10.1103/PhysRevA.37.2467
  5. 5.
    Frisch MJ, Pople JA, Krishnan R, Binkley JS (1984) J Chem Phys 80:3265. doi:10.1063/1.447079 CrossRefGoogle Scholar
  6. 6.
    Barone V, Peralta RH, Contreras RH, Snyder JP (2002) J Phys Chem 106:5607Google Scholar
  7. 7.
    Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery Jr JA, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Adao C, Jaramill, J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA (2003) Gaussian 03. Gaussian, Inc., Pittsburgh, PAGoogle Scholar
  8. 8.
    (a) Bader RFW (1990) Atoms in molecules: a quantum theory. Clarendon Press, Oxford; (b) Popelier PLA (2000) Atoms in molecules. An introduction. Prentice Hall, Harlow, EnglandGoogle Scholar
  9. 9.
    Biegler-König FW, Bader RFW, Tang TH (1982) J Comput Chem 3:317. doi:10.1002/jcc.540030306 CrossRefGoogle Scholar
  10. 10.
    Biegler-König FW, Schönbom J (2002) AIM2000, 2nd edn. Bielefeld, GermanyGoogle Scholar
  11. 11.
    (a) Miertus S, Scrocco E, Tomasi J (1981) Chem Phys 55:117. doi:10.1016/0301-0104(81)85090-2; (b) Mennucci B, Cammi R (eds) (2007) Continuum solvation models in chemical physics. From theory to applications. Wiley, Chichester
  12. 12.
    Beak P, Meyers AI (1986) Acc Chem Res 19:356. doi:10.1021/ar00131a005 CrossRefGoogle Scholar
  13. 13.
    Whisler MC, MacNeil S, Snieckus V, Beak P (2004) Angew Chem Int Ed 43:2206. doi:10.1002/anie.200300590 CrossRefGoogle Scholar
  14. 14.
    Sygula A, Rabideau PW (1992) J Am Chem Soc 114:821. doi:10.1021/ja00029a003 CrossRefGoogle Scholar
  15. 15.
    Blanco F, O’Donovan DH, Alkorta I, Elguero J (2008) Struct Chem. doi:10.1007/s11224-008-9290-2
  16. 16.
    Matta CF, Hernández-Trujillo J, Tang TH, Bader RFW (2003) Chem Eur J 9:1940. doi:10.1002/chem.200204626 CrossRefGoogle Scholar
  17. 17.
    Blanco F, Alkorta I, Elguero J (2007) Magn Reson Chem 45:797. doi:10.1002/mrc.2053 CrossRefGoogle Scholar
  18. 18.
    Alkorta I, Elguero J (1998) Struct Chem 9:187. doi:10.1023/A:1022419030317 CrossRefGoogle Scholar
  19. 19.
    (a) McKeever LD, Waack R, Doran MA, Baker EB (1968) J Am Chem Soc 90:3244. doi:10.1021/ja01014a051; (b) McKeever LD, Waack R, Doran MA, Baker EB (1969) J Am Chem Soc 91:1057. doi:10.1021/ja01033a003; (c) Clark T, Chandrasekhar J, Schleyer Pv R (1980) Chem Commun 672; (d) Bauer W, Winchester WR, Schleyer Pv R (1987) Organometallics 6:2371. doi:10.1021/om00154a017; (e) Harder S, Boersma J, Brandsma L, Kanters JA, Bauer W (1696) Schleyer PvR (1989) Organometallics 8
  20. 20.
    Kwon O, Sevin F, McKee ML (2001) J Phys Chem A 105:913. doi:10.1021/jp003345c CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2008

Authors and Affiliations

  • Vito Capriati
    • 1
  • Saverio Florio
    • 1
  • Renzo Luisi
    • 1
  • Biagia Musio
    • 1
  • Ibon Alkorta
    • 2
  • Fernando Blanco
    • 2
  • José Elguero
    • 2
  1. 1.Dipartimento Farmaco-ChimicoUniversità di BariBariItaly
  2. 2.Instituto de Química Médica (CSIC)MadridSpain

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