Theoretical Chemistry Accounts

, Volume 119, Issue 1–3, pp 133–142 | Cite as

Direct determination of absolute configuration: a vibrational circular dichroism study on dimethyl-substituted phenyloxiranes synthesized by Shi epoxidation

  • Peter Fristrup
  • Peter Rygaard Lassen
  • David Tanner
  • K. J. Jalkanen
Regular Article

Abstract

The three possible dimethylsubstituted phenyloxiranes (cis, trans and geminal) were synthesized in both racemic (mCPBA) and enantiomerically enriched forms (Shi epoxidation) and subjected to a vibrational circular dichroism study. The experimental spectra were compared to theoretical spectra obtained using DFT/B3LYP calculations, and the differences between experiment and theory are discussed. The absolute configuration at the benzylic position was established as being (R), (S) and (R) for the cis, trans and geminal dimethylsubstituted phenyloxiranes, respectively. In all three cases the configuration of the major enantiomer was in accordance with a simple transition state model based on the spiro reaction mode.

Keywords

Vibrational circular dichroism DFT calculations Epoxidation Asymmetric catalysis Absolute configuration 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

Supplementary material

References

  1. 1.
    Jacobsen EN (2000) . Acc Chem Res 33:421CrossRefGoogle Scholar
  2. 2.
    Taylor SK (2000) . Tetrahedron 56:1149CrossRefGoogle Scholar
  3. 3.
    Hanson RM (1991) . Chem Rev 91:437CrossRefGoogle Scholar
  4. 4.
    Pfenninger A (1986) Synthesis 89Google Scholar
  5. 5.
    Behrens CH, Sharpless KB (1983) . Aldrichimica Acta 16:67Google Scholar
  6. 6.
    Besse P, Veschambre H (1994) . Tetrahedron 50:8885CrossRefGoogle Scholar
  7. 7.
    Katsuki T, Sharpless KB (1980) . J Am Chem Soc 102:5974CrossRefGoogle Scholar
  8. 8.
    Johnson RA, Sharpless KB (2000) In: Ojima I (ed) Catalytic asymmetric synthesis, Chap. 6A, 2nd edn. Wiley-VCH, New YorkGoogle Scholar
  9. 9.
    Zhang W, Loebach JL, Wilson SR, Jacobsen EN (1990) . J Am Chem Soc 112:2801CrossRefGoogle Scholar
  10. 10.
    Jacobsen EN, Wu MH (1999) In: Jacobsen EN, Pfaltz A, Yamamoto H (eds) Comprehensive asymmetric catalysis, Chap. 18.2. Springer, Berlin Heidelberg New YorkGoogle Scholar
  11. 11.
    Irie R, Noda K, Ito Y, Matsumoto N, Katsuki T (1990) . Tetrahedron Lett 31:7345CrossRefGoogle Scholar
  12. 12.
    Katsuki T (2000) In: Ojima I (ed) Catalytic asymmetric synthesis, Chap. 6B, 2nd edn. Wiley-VCH, New YorkGoogle Scholar
  13. 13.
    Shi Y (2004) . Acc Chem Res 37:488CrossRefGoogle Scholar
  14. 14.
    Wang Z-X, Tu Y, Frohn M, Zhang J-R, Shi Y (1997) . J Am Chem Soc 119:11224CrossRefGoogle Scholar
  15. 15.
    Wang Z-X, Tu Y, Frohn M, Shi Y (1997) . J Org Chem 62:2328CrossRefGoogle Scholar
  16. 16.
    Tu Y, Wang Z-X, Shi Y (1996) . J Am Chem Soc 118:9806CrossRefGoogle Scholar
  17. 17.
    Wang Z-X, Miller SM, Anderson OP, Shi Y (1999) . J Org Chem 64:6433Google Scholar
  18. 18.
    Tu Y, Wang Z-X, Frohn M, He M, Yu H, Tang Y, Shi Y (1998) . J Org Chem 63:8475CrossRefGoogle Scholar
  19. 19.
    Shu L, Wang P, Gan Y, Shi Y (2003) . Org Lett 5:293CrossRefGoogle Scholar
  20. 20.
    Tian H, She X, Shi Y (2001) . Org Lett 3:715CrossRefGoogle Scholar
  21. 21.
    Tian H, She X, Shu L, Yu H, Shi Y (2000) . J Am Chem Soc 122:11551CrossRefGoogle Scholar
  22. 22.
    Tian H, She X, Xu J, Shi Y (2001) . Org Lett 3:1929CrossRefGoogle Scholar
  23. 23.
    Singleton DA, Wang Z (2005) . J Am Chem Soc 127:6679CrossRefGoogle Scholar
  24. 24.
    Fristrup P, Lassen PR, Johannesen C, Tanner D, Norrby P-O, Jalkanen KJ, Hemmingsen L (2006) . J Phys Chem A 110:9123CrossRefGoogle Scholar
  25. 25.
    The visualizations have been performed using Jmol, An OpenScience Project, © 2004 by the Jmol Team, see also http://www.jmol.sourceforge.netGoogle Scholar
  26. 26.
    Jalkanen KJ, Würtz Jürgensen V, Degtyarenko IM (2005) . Adv Quant Chem 50:91CrossRefGoogle Scholar
  27. 27.
    Ashvar CS, Devlin FJ, Stephens PJ (1999) . J Am Chem Soc 121:2836CrossRefGoogle Scholar
  28. 28.
    Molecular modelling was carried out in MacroModel v. 8.0 from Schrodinger Inc., http://www. schrodinger.com.Google Scholar
  29. 29.
    Jaguar 4.2, Schrödinger, Inc., 1500 SW First Avenue, Suite 1180, Portland, OR 97201. For the most recent version, see: Schrodinger Inc. (http://www.schrodinger.com)Google Scholar
  30. 30.
    Clark T, Chandrasekhar J, Spitznagel GW, Schleyer PvR (1983) . J Comp Chem 4:294CrossRefGoogle Scholar
  31. 31.
    Hehre WJ, Ditchfield R, Pople JA (1972) . J Chem Phys 56:2257CrossRefGoogle Scholar
  32. 32.
    Ditchfield R, Hehre WJ, Pople JA (1971) . J Chem Phys 54:724CrossRefGoogle Scholar
  33. 33.
    Gaussian 03, Revision C.02, Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA Jr, 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, Bakken V, Adamo C, Jaramillo 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 (2004) Gaussian, Inc., WallingfordGoogle Scholar
  34. 34.
    Halgren TA (1996) . J Comput Chem 17:490CrossRefGoogle Scholar
  35. 35.
    MacroModel v. 8.0 from Schrodinger Inc.: Mohamadi F, Richards NGJ, Guida WC, Liskamp R, Lipton M, Caulfield C, Chang G, Hendrickson T, Still WC (1990) J Comput Chem 11:440. For current versions, see: http://www.schrodinger.comGoogle Scholar
  36. 36.
    Razuvaev GA et al. (1965) . J Org Chem USSR (Engl Transl) 1:1589–1591Google Scholar
  37. 37.
    Fristrup P, Tanner D, Norrby P-O (2003) . Chirality 15:360CrossRefGoogle Scholar
  38. 38.
    Fristrup P, Dideriksen BD, Tanner D, Norrby P-O (2005) . J Am Chem Soc 127:13672CrossRefGoogle Scholar
  39. 39.
    Satoh T, Kobayashi S, Nakanishi S, Horiguchi K, Irisa S (1999) . Tetrahedron 55:2515CrossRefGoogle Scholar
  40. 40.
    Pedragosa-Moreau S, Archelas A, Furstoss R (1996) . Tetrahedron 52:4593CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2006

Authors and Affiliations

  • Peter Fristrup
    • 1
    • 2
  • Peter Rygaard Lassen
    • 3
  • David Tanner
    • 2
  • K. J. Jalkanen
    • 3
    • 4
  1. 1.Center for Sustainable and Green Chemistry, Department of ChemistryTechnical University of DenmarkLyngbyDenmark
  2. 2.Department of ChemistryTechnical University of DenmarkLyngbyDenmark
  3. 3.The Quantum Protein Centre, Department of PhysicsTechnical University of DenmarkLyngbyDenmark
  4. 4.Nanochemistry Research Institute, Department of Applied ChemistryCurtin University of TechnologyPerthAustralia

Personalised recommendations