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The Mechanism of Epoxide Opening through Electron Transfer: Experiment and Theory in Concert

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Radicals in Synthesis I

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 263))

Abstract

This review gives a description of the mechanism of reductive epoxide opening through single-electron transfer. A number of electron-transfer reagents are compared and the most promising titanocene complexes are studied in detail. The mechanism of epoxide opening was established by cyclic voltammetry, kinetic measurements, DFT calculations, and synthetic studies. The results are used to devise more selective reagents.

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Abbreviations

B-P functional:

Becke–Perdew functional

Coll:

2,4,6-Collidine

Cp:

Cyclopentadienyl

CV:

Cyclic voltammetry

DFT:

Density functional theory

DMF:

N,N -Dimethylformamide

dr:

Diastereomeric ratio

equiv.:

Equivalents

ET:

Electron transfer

EtOAc:

Ethyl acetate

THF:

Tetrahydrofuran

TZVP:

Triple-zeta valence polarization

References

  1. Lane BS, Burgess K (2003) Chem Rev 103:2457

    Article  CAS  Google Scholar 

  2. McGarrigle EM, Gilheany DC (2005) Chem Rev 105:1564

    Article  CAS  Google Scholar 

  3. Jacobsen EN (2000) Acc Chem Res 33:421

    Article  CAS  Google Scholar 

  4. Gansäuer A, Bluhm H (2000) Chem Rev 100:2771

    Article  Google Scholar 

  5. Gansäuer A, Lauterbach T, Narayan S (2003) Angew Chem Int Ed 42:5556

    Article  Google Scholar 

  6. Birch AJ (1949) J Proc R Soc NSW 83:245

    Google Scholar 

  7. Hallsworth AS, Henbest HB (1957) J Chem Soc 4604

    Google Scholar 

  8. Brown HC, Ikegami S, Kawakami JH (1970) J Org Chem 35:3243

    Article  CAS  Google Scholar 

  9. Benkesser RA, Rappa A, Wolsieffer LA (1986) J Org Chem 51:3391

    Article  Google Scholar 

  10. Bartmann E (1986) Angew Chem Int Ed 25:653

    Article  Google Scholar 

  11. Dorigo AE, Houk KN, Cohen T (1989) J Am Chem Soc 111:8976

    Article  CAS  Google Scholar 

  12. Conrow RE (1993) Tetrahedron Lett 34:5533

    Article  Google Scholar 

  13. Bachki A, Foubeto F, Yus M (1995) Tetrahedron Asymmetry 6:1907

    Article  CAS  Google Scholar 

  14. Bachki A, Foubeto F, Yus M (1996) Tetrahedron Asymmetry 7:2997

    Article  CAS  Google Scholar 

  15. Cox JD, Pilcher G (eds) (1970) Thermochemistry of organic and organometallic compounds. Academic, London

    Google Scholar 

  16. Seeman JI (1983) Chem Rev 83:83

    Article  CAS  Google Scholar 

  17. Nugent WA, RajanBabu TV (1998) J Am Chem Soc 110:8561

    Article  Google Scholar 

  18. RajanBabu TV, Nugent WA (1989) J Am Chem Soc 111:4525

    Article  CAS  Google Scholar 

  19. RajanBabu TV, Nugent WA, Beattie MS (1990) J Am Chem Soc 112:6408

    Article  CAS  Google Scholar 

  20. RajanBabu TV, Nugent WA (1994) J Am Chem Soc 116:986

    Article  CAS  Google Scholar 

  21. Halgren TH, Roberts JD, Horner JH, Martinez F, Tronche C, Newcomb M (2000) J Am Chem Soc 122:2988

    Article  CAS  Google Scholar 

  22. Friedrich J, Dolg M, Gansäuer A, Geich-Gimbel D, Lauterbach T (2005) J Am Chem Soc 127:7071

    Article  CAS  Google Scholar 

  23. Sharpless KB, Umbreit MA, Nieh MT, Flood TC (1972) J Am Chem Soc 94:6538

    Article  CAS  Google Scholar 

  24. Su H, Walder L, Zhang Zd, Scheffold R (1988) Helv Chim Acta 71:1073

    Article  CAS  Google Scholar 

  25. Bonhote P, Scheffold R (1991) Helv Chim Acta 74:1425

    Article  CAS  Google Scholar 

  26. Gansäuer A, Rinker B (2002) Tetrahedron 58:7017

    Article  Google Scholar 

  27. Matsukawa M, Tabuchi T, Inanaga J, Yamaguchi M (1987) Chem Lett 2101

    Google Scholar 

  28. Manzer LE (1982) Inorg Synth 21:135

    Article  CAS  Google Scholar 

  29. Freudenberger JH, Konradi AW, Pedersen SF (1989) J Am Chem Soc 111:8014

    Article  CAS  Google Scholar 

  30. Konradi AW, Kemp SJ, Pedersen SF (1994) J Am Chem Soc 116:1316

    Article  CAS  Google Scholar 

  31. Konradi AW, Pedersen SF (1992) J Org Chem 57:28

    Article  CAS  Google Scholar 

  32. Reetz MT, Griebenow N (1996) Liebigs Ann Chem 335

    Google Scholar 

  33. Kammermeier B, Beck G, Holla W, Jacobi D, Napierski B, Jendralla H (1996) Chem Eur J 2:307

    Article  CAS  Google Scholar 

  34. Kochi JK, Singleton DM, Andrews LJ (1968) Tetrahedron 24:3503

    Article  CAS  Google Scholar 

  35. Molander GA (2001) In: Renaud P, Sibi MP (eds) Radicals in organic synthesis, vol 1. Wiley, Weinheim, p 153 and references cited therein

    Google Scholar 

  36. Hasegawa E, Curran DP (1993) Tetrahedron Lett 34:1717

    Article  CAS  Google Scholar 

  37. Shabangi M, Kuhlman ML, Flowers RA II (1999) Org Lett 1:2133

    Article  CAS  Google Scholar 

  38. Enemærke RJ, Hertz T, Skrydstrup T, Daasbjerg K (2000) Chem Eur J 6:3747

    Article  Google Scholar 

  39. Beckwith ALJ, Schiesser C (1985) Tetrahedron 41:3925

    Article  CAS  Google Scholar 

  40. Schiesser CH, Wild LM (1996) Tetrahedron 42:13265

    Article  Google Scholar 

  41. Walton JC (1998) Acc Chem Res 31:99

    Article  CAS  Google Scholar 

  42. Curran DP, Fevig TL, Jasperse CP, Totleben MJ (1992) Synlett 943

    Google Scholar 

  43. Krief A, Laval AM (1999) Chem Rev 99:745

    Article  CAS  Google Scholar 

  44. Wild FRW, Zsolnai L, Huttner G, Brintzinger HH (1982) J Organomet Chem 232:233

    Article  CAS  Google Scholar 

  45. Collins S, Kuntz BA, Taylor NJ, Ward DG (1988) J Organomet Chem 342:21

    Article  CAS  Google Scholar 

  46. Jaquith JB, Guan J, Wang S, Collins S (1995) Organometallics 14:1079

    Article  CAS  Google Scholar 

  47. Cesarotti E, Kagan HB, Goddard R, Krüger C (1978) J Organomet Chem 162:297

    Article  CAS  Google Scholar 

  48. Pedersen SU, Daasbjerg K (2001) In: Balzani V (ed) Electron transfer in chemistry, vol 1. Wiley, Weinheim, p 422

    Chapter  Google Scholar 

  49. Enemærke RJ, Larsen J, Skrydstrup T, Daasbjerg K (2004) Organometallics 23:1866

    Article  CAS  Google Scholar 

  50. Enemærke RJ, Larsen J, Skrydstrup T, Daasbjerg K (2004) J Am Chem Soc 126:7853

    Article  CAS  Google Scholar 

  51. Enemærke RJ, Larsen J, Hjøllund GH, Skrydstrup T, Daasbjerg K (2005) Organometallics 24:1252

    Article  CAS  Google Scholar 

  52. Mendes P, Gepasi, version 3.21. Virginia Tech, Blacksburg, VA. http://www.gepasi.org

  53. Sekutowski DJ, Stucky GD (1975) Inorg Chem 14:2192

    Article  CAS  Google Scholar 

  54. Sekutowski DJ, Jungst R, Stucky GD (1978) Inorg Chem 17:1848

    Article  CAS  Google Scholar 

  55. Negishi EI (1999) Chem Eur J 5:411

    Article  CAS  Google Scholar 

  56. Ahlrichs R, Bär M, Baron HP, Bauernschmitt R, Böcker S, Ehrig M, Eichkorn K, Elliott S, Furche F, Haase F, Häser M, Horn H, Huber C, Huniar U, Kattannek M, Kölmel C, Kollwitz M, May K, Ochsenfeld C, Öhm H, Schäfer A, Schneider U, Treutler O, von Arnim M, Weigend F, Weis F, Weiss H (2000) TURBOMOLE Version 5.3, Universität Karlsruhe

    Google Scholar 

  57. Becke AD (1988) Phys Rev A 38:3098

    Article  CAS  Google Scholar 

  58. Schäfer A, Horn H, Ahlrichs R (1992) J Chem Phys 97:2571

    Article  Google Scholar 

  59. Gansäuer A, Lauterbach T, Bluhm H, Noltemeyer M (1999) Angew Chem Int Ed 38:2909

    Article  Google Scholar 

  60. Gansäuer A, Bluhm H, Rinker B, Narayan S, Schick M, Lauterbach T, Pierobon M (2003) Chem Eur J 9:531

    Article  Google Scholar 

  61. Gansäuer A, Rinker B, Pierobon M, Grimme S, Gerenkamp M, Mück-Lichtenfeld C (2003) Angew Chem Int Ed 42:3687

    Article  Google Scholar 

  62. Gansäuer A, Rinker B, Ndene-Schiffer N, Pierobon M, Grimme S, Gerenkamp M, Mück-Lichtenfeld C (2004) Eur J Org Chem :2337

    Google Scholar 

  63. Mudryk B, Cohen T (1991) J Am Chem Soc 113:1866

    Article  CAS  Google Scholar 

  64. Malacria M (1996) Chem Rev 96:289

    Article  CAS  Google Scholar 

  65. Gansäuer A, Pierobon M, Bluhm H (1998) Angew Chem Int Ed 37:101

    Article  Google Scholar 

  66. Gansäuer A, Bluhm H, Pierobon M (1998) J Am Chem Soc 120:12849

    Article  Google Scholar 

  67. Berno P, Floriani C, Chiesi-Villa A, Guastini C (1990) Organometallics 9:1995

    Article  CAS  Google Scholar 

  68. Hortmann K, Diebold J, Brintzinger HH (1993) J Organomet Chem 445:107

    Article  CAS  Google Scholar 

  69. Curtis MD, Thanedar S, Butler WM (1984) Organometallics 3:1855

    Article  CAS  Google Scholar 

  70. Spellmeyer DC, Houk KN (1987) J Org Chem 52:959

    Article  CAS  Google Scholar 

  71. Isaacs N (1995) Physical organic chemistry, 2nd edn. Longman, Harlow, p 418

    Google Scholar 

  72. Hammond GS (1955) J Am Chem Soc 77:334

    Article  CAS  Google Scholar 

  73. Gansäuer A, Pierobon M (2000) Synlett 1357

    Google Scholar 

  74. Gansäuer A, Pierobon M, Bluhm H (2001) Synthesis 2500

    Google Scholar 

  75. Barrero AF, Rosales A, Cuerva JM, Oltra E (2003) Org Lett 5:1935

    Article  CAS  Google Scholar 

  76. Justicia J, Rosales A, Buñuel E, Oller-López JL, Valdivia M, Haïdour A, Oltra JE, Barrero AF, Cárdenas DJ, Cuerva JM (2004) Chem Eur J 10:1778

    Article  CAS  Google Scholar 

  77. Schreiber SL (2000) Science 287:1964

    Article  CAS  Google Scholar 

  78. Lee D, Sello JK, Schreiber SL (2000) Org Lett 2:709

    Article  CAS  Google Scholar 

  79. Bailey WF, Longstaff SC (2001) Org Lett 3:2217

    Article  CAS  Google Scholar 

  80. Trost BM, Crawley ML (2003) Chem Rev 103:2921

    Article  CAS  Google Scholar 

Download references

Acknowledgments

We are grateful for continued financial support by the Danish Natural Science Research Council, the Deutsche Forschungsgemeinschaft, the Alexander von Humboldt-Stiftung, and the Fonds der Chemischen Industrie

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Aarhus, Langelandsgade 140, 8000, Aarhus C, Denmark

    Kim Daasbjerg & Heidi Svith

  2. Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Correnstr. 40, 49149, Münster, Germany

    Stefan Grimme, Mareike Gerenkamp & Christian Mück-Lichtenfeld

  3. Kekulé Institut für Organische Chemie und Biochemie, Universität Bonn, Gerhard-Domagk-Str. 1, 53121, Bonn, Germany

    Andreas Gansäuer & Andriy Barchuk

Authors
  1. Kim Daasbjerg
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  2. Heidi Svith
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  4. Mareike Gerenkamp
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  5. Christian Mück-Lichtenfeld
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Correspondence to Kim Daasbjerg , Stefan Grimme or Andreas Gansäuer .

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Andreas Gansäuer

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Daasbjerg, K. et al. The Mechanism of Epoxide Opening through Electron Transfer: Experiment and Theory in Concert. In: Gansäuer, A. (eds) Radicals in Synthesis I. Topics in Current Chemistry, vol 263. Springer, Berlin, Heidelberg. https://doi.org/10.1007/128_020

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