Skip to main content

Catalytic Ring-Closing Metathesis and the Development of Enantioselective Processes

  • Chapter
  • First Online:
Alkene Metathesis in Organic Synthesis

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 1))

Abstract

Catalytic ring-closing metathesis makes available a wide range of cyclic alkenes, thus rendering a number of stereoselective olefin functionalizations practical. The availability of effective metathesis catalysts has also spawned the development of a variety of methods that prepare specially-outfitted diene substrates that can undergo catalytic ring closure. The new metathesis catalysts have already played a pivotal role in a number of enantioselective total syntheses.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 84.99
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 109.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References and Footnotes

  1. For recent reviews on olefin metathesis in organic synthesis, see: (a) Grubbs RH, Miller SJ, Fu GC (1995) Acc Chem Res 28:446 and references cited therein.

    Article  CAS  Google Scholar 

  2. Schmalz H-G (1995) Angew Chem, Int Ed Engl 107:1833 and references cited therein.

    Article  Google Scholar 

  3. Schuster M, Blechert S (1997) Angew Chem, Int Ed Engl 36:2036. For initial pioneering studies on olefin metathesis, see

    Article  Google Scholar 

  4. Katz TJ, Lee SJ, Acton N (1976) Tetrahedron Lett 4247.

    Google Scholar 

  5. Katz TJ, Acton N (1976) Tetrahedron Lett 4241.

    Google Scholar 

  6. Katz TJ, McGinnis J, Altus C (1976) J Am Chem Soc 98:606.

    Article  CAS  Google Scholar 

  7. Katz TJ (1977) Adv Organomet Chem 16:283.

    Article  CAS  Google Scholar 

  8. Tsuji J, Hashiguchi S (1980) Tetrahedron Lett 21: 2955

    Article  CAS  Google Scholar 

  9. Fu GC, Grubbs RH (1992) J Am Chem Soc 114:7324.

    Article  CAS  Google Scholar 

  10. Fu GC, Grubbs RH (1993) J Am Chem Soc 115:3800.

    Article  CAS  Google Scholar 

  11. Wu Z, Nguyen ST, Grubbs RH, Ziller JW (1995) J Am Chem Soc 117:5503

    Article  CAS  Google Scholar 

  12. Schrock RR, Murdzek JS, Bazan GC, Robbins J, DiMare M, O’Regan M ( 1990) J Am Chem Soc 112:3875.

    Article  CAS  Google Scholar 

  13. Bazan GC, Schrock RR, Cho H-N, Gibson VC (1991) Macromolecules 24:4495

    Article  CAS  Google Scholar 

  14. Morken JP, Didiuk MT, Hoveyda AH (1993) J Am Chem Soc 115:6697.

    Google Scholar 

  15. Didiuk MT, Johannes CW, Morken JP ( 1995) J Am Chem Soc 117:7097. For a recent review, see: Hoveyda AH, Morken JP (1996) Angew Chem, Int Ed Engl 35:1262

    Article  CAS  Google Scholar 

  16. Morken JP, Didiuk MT, Visser MS, Hoveyda AH (1994) J Am Chem Soc 116:3123.

    Article  CAS  Google Scholar 

  17. Visser MS, Hoveyda AH (1995) Tetrahedron 51:4383.

    Article  CAS  Google Scholar 

  18. Visser MS, Harrity JPA, Hoveyda AH (1996) J Am Chem Soc 118:3779.

    Article  CAS  Google Scholar 

  19. Visser MS, Heron NM, Didiuk MT, Sagal JF, Hoveyda AH ( 1996) J Am Chem Soc 118:4291

    Article  CAS  Google Scholar 

  20. Miller SJ, Kim S, Chen Z, Grubbs RH (1995) J Am Chem Soc 117:2108.

    Article  CAS  Google Scholar 

  21. Miller SJ, Grubbs RH (1995) J Am Chem Soc 117:5855.

    Article  CAS  Google Scholar 

  22. Houri AF, Xu Z, Cogan DA, Hoveyda AH (1995) J Am Chem Soc 117:2943

    Article  CAS  Google Scholar 

  23. For a discussion of the Thorpe-Ingold effect, see: Eliel E, Wilen SH, (1994) Stereochemistry of organic compounds, 1st edn. Wiley Interscience, New York, p 682

    Google Scholar 

  24. For a related recent report, see: (a) Linderman RJ, Siedlecki J, O’Neill SA, Sun H (1997) J Am Chem Soc 119:6919.

    Article  CAS  Google Scholar 

  25. Furstner A, Muller T (1997) Synlett 1010

    Google Scholar 

  26. For two examples of this type of resolution (the first two involve transition metal catalysis), see: (a) Hayashi T, Yamamoto M (1987) Chem Lett 177.

    Google Scholar 

  27. Martin SF, Spaller MR, Liras S, Hartmann B (1994) J Am Chem Soc 116:4493.

    Article  CAS  Google Scholar 

  28. Vedejs E, Chen X (1997) J Am Chem Soc 119:2584

    Article  CAS  Google Scholar 

  29. For a review of directed reactions, see: Hoveyda AH, Evans DA, Fu GC (1993) Chem Rev 93:1307

    Article  Google Scholar 

  30. Heron NM, Adams JA, Hoveyda AH (1997) J Am Chem Soc 119:6205

    Article  CAS  Google Scholar 

  31. Heron NM, Adams JA, Hoveyda AH (1998) manuscript in preparation

    Google Scholar 

  32. Harrity JPA, Visser MS, Gleason JD, Hoveyda AH (1997) J Am Chem Soc 119:1488.

    Article  CAS  Google Scholar 

  33. Harrity JPA, La DS, Cefalo DR, Visser MS, Hoveyda AH (1998) J Am Chem Soc 120:2343

    Article  CAS  Google Scholar 

  34. Crowe WE, Zhang ZJ (1993) J Am Chem Soc 115:10998.

    Article  CAS  Google Scholar 

  35. Crowe WE, Goldberg DR (1995) J Am Chem Soc 117:5162.

    Article  CAS  Google Scholar 

  36. Crowe WE, Goldberg DR, Zhang ZJ (1996) Tetrahedron Lett 37:2117

    Article  CAS  Google Scholar 

  37. Kim S, Chen Z, Grubbs RH (1995) J Am Chem Soc 117:2108 Ref. 6a.

    Article  CAS  Google Scholar 

  38. Marsella MJ, Maynard HD, Grubbs RH (1997) Angew Chem, Int Ed Engl 36:1101 and references cited therein

    Article  CAS  Google Scholar 

  39. For a recent report on the mechanism of the Ru-catalyzed ring-closing metathesis, see: Dias EL, Nguyen ST, Grubbs RH (1997) J Am Chem Soc. 119:3887

    Article  Google Scholar 

  40. Schwab P, Grubbs RH, Ziller JW (1996) J Am Chem Soc 118:100

    Article  CAS  Google Scholar 

  41. For a study on the ring-opening metathesis of cyclohexene, see: Patton PA, Lillya CP, McCarthy TJ (1986) Macromolecules 19:1266

    Article  Google Scholar 

  42. For a hydroxyl-directed olefination of ketones with 2 as catalyst, see: Fujimura O, Fu GC, Rothemund PWK, Grubbs RH (1995) J Am Chem Soc 117:2355

    Article  Google Scholar 

  43. For the Mn-catalyzed kinetic resolution of 2,2-disubstituted chromenes, see: Vander Velde SL, Jacobsen EN (1995) J Org Chem 60:5380

    Article  Google Scholar 

  44. Van Lommen G, De Bruyn M, Schroven M (1990) J Pharm Belg 45:355 and references cited therein

    Google Scholar 

  45. Johannes CW, Visser MS, Weatherhead GA, Hoveyda AH (1998) J Am Chem Soc in press

    Google Scholar 

  46. Xu Z, Johannes CW, Houri AF, La DS, Cogan DA, Hofilena GE, Hoveyda AH (1997) J Am Chem Soc 119:10302 and references cited therein

    Article  CAS  Google Scholar 

  47. Corey EJ, Hopkins PB, Kim S, Yoo S-E, Nambia KP, Falck JR (1979) J Am Chem Soc 101:7131.

    Article  CAS  Google Scholar 

  48. Still WC, Galynker I (1981) Tetrahedron 37:3981.

    Article  CAS  Google Scholar 

  49. Schreiber SL, Santini C (1984) J Am Chem Soc 106:4038.

    Article  CAS  Google Scholar 

  50. Neeland EG, Ounsworth JP, Sims RJ, Weiler L (1994) J Org Chem 58:7383.

    Article  Google Scholar 

  51. Evans DA, Ratz AM, Huff BE, Sheppard GS ( 1995) J Am Chem Soc 117:3448

    Article  CAS  Google Scholar 

  52. Martin SF, Liao Y, Wong Y, Rein T (1994) Tetrahedron Lett 35:691

    Article  CAS  Google Scholar 

  53. Borer BC, Deerenberg S, Bieraugel H, Pandit UK (1994) Tetrahedron Lett 35:3191

    Article  CAS  Google Scholar 

  54. Martin SF, Liao Y, Chen H-J, Patzel M, Ramser MN (1994) Tetrahedron Lett 35:6005

    Article  CAS  Google Scholar 

  55. For a classic example, see: Woodward RB, et. al. (1981) J Am Chem Soc 103:3213

    Article  Google Scholar 

  56. Recent studies by Grubbs on the effect of stereochemistry on synthesis of macrocyclic peptides (disubstituted alkenes) by ring closing metathesis were not disclosed at the time of our planning. See: (a)Kim S, Chen Z, Grubbs RH (1995) J Am Chem Soc 117:2108 Ref. 6a.

    Article  Google Scholar 

  57. Miller SJ, Blackwell H, Grubbs RH (1996) J Am Chem Soc 118:9606

    Article  CAS  Google Scholar 

  58. As recently demonstrated by Furstner and Langemann, higher yields of the disubstituted olefin 83 can be obtained under high dilution conditions using 1a as the catalyst. Our experiments clearly illustrate that synthesis of trisubstituted macrocyclic alkenes is more complicated than that of their disubstituted analogues. See: Furstner A, Langemann K (1996) J Org Chem 61:3942

    Article  Google Scholar 

  59. Bertinato P, Sorensen EJ, Meng D, Danishefsky SJ (1996) J Org Chem 61:8000.

    Article  CAS  Google Scholar 

  60. Meng D, Su D-S, Balog A, Bertinato P, Sorensen EJ, Danishefsky SJ, Zheng Z-H, Chou T-C, He L, Horwitz SB (1997) J Am Chem Soc 119:2733.

    Article  CAS  Google Scholar 

  61. Meng D, Bertinato P, Balog A, Su D-S, Kamenecka T, Sorensen EJ, Danishefsky SJ (1997) J Am Chem Soc 119:10073

    Article  CAS  Google Scholar 

  62. Nicolaou KC, He Y, Vourloumis D, Vallberg H, Yang Z (1996) Angew Chem, Int Ed Engl 35:2399.

    Article  CAS  Google Scholar 

  63. Yang Z, He Y, Vourloumis D, Vallberg H, Nicolaou KC (1997) Angew Chem, Int Ed Engl 36:166.

    Article  CAS  Google Scholar 

  64. Nicolaou KC, Sarabia F, Ninkovic S, Yang Z (1997) Angew Chem, Int Ed Engl 36:525.

    Article  CAS  Google Scholar 

  65. Nicolaou KC, Winssinger N, Pastor J, Ninkovic S, Sarabia F, He Y, Vourloumis D, Yang Z, Li T, Giannakakou P, Hamel E (1997) Nature 387:268

    Article  CAS  Google Scholar 

  66. Kim SH, Figueroa I, Fuchs PL (1997) Tetrahedron Lett 38:2601

    Article  CAS  Google Scholar 

  67. Furstner A, Kindler K (1996) Tetrahedron Lett 37:7005

    Article  Google Scholar 

  68. Furstner A, Langemann K ( 1997) J Am Chem Soc 119:9130.

    Article  Google Scholar 

  69. Furstner A, Langemann K (1997) Synthesis 792

    Google Scholar 

  70. Schinzer D, Limberg A, Bauer A, Bohm OM, Cordes M (1997) Angew Chem, Int Ed Engl 36:523

    Article  CAS  Google Scholar 

  71. More recent accounts from the laboratories of Grubbs and Sauvage indicate that the metathesis technology may be readily applied to the synthesis of macrocyclic crown ethers and [2]catenanes. See: (a)Maynard HD, Grubbs RH (1997) Angew Chem, Int Ed Engl 36:1101 Ref. 17b.

    Article  Google Scholar 

  72. Mohr B, Weck M, Sauvage J-P, Grubbs RH (1997) Angew Chem, Int Ed Engl 36:1308

    Article  CAS  Google Scholar 

  73. For recent examples, where 1a has been used in the development of new reaction methods, see: (a) Clark TD, Ghadiri MR (1995) J Am Chem Soc 117:12364.

    Article  CAS  Google Scholar 

  74. Tallarico JA, Randall ML, Snapper ML (1996) J Am Chem Soc 38:9196.

    Article  Google Scholar 

  75. Kim S-H, Zuercher WJ, Bowden NB, Grubbs RH (1996) J Am Chem Soc 118:1073.

    Article  Google Scholar 

  76. Snapper ML, Tallarico JA, Randall ML (1997) J Am Chem Soc 119:1478.

    Article  CAS  Google Scholar 

  77. Piscopio AD, Miller JF, Koch K (1997) Tetrahedron Lett 38:7143.

    Article  CAS  Google Scholar 

  78. Kinoshita A, Sakakibara N, Mori M (1997) J Am Chem Soc 119:12388.

    Article  CAS  Google Scholar 

  79. Crimmins MT, Choy AL (1997) J Org Chem 62:7548

    Article  CAS  Google Scholar 

  80. For a recent report on Mo-catalyzed enantioselective RCM, see: Alexander JB, La DS, Cefalo DR, Hoveyda AH, Schrock RR (1998) J Am Chem Soc 120:4041 and references cited therein

    Article  Google Scholar 

Download references

Authors

Editor information

Editors and Affiliations

Rights and permissions

Reprints and permissions

Copyright information

© 1998 Springer-Verlag Berlin Heidelberg

About this chapter

Cite this chapter

Hoveyda, A.H. (1998). Catalytic Ring-Closing Metathesis and the Development of Enantioselective Processes. In: Fürstner, A. (eds) Alkene Metathesis in Organic Synthesis. Topics in Organometallic Chemistry, vol 1. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-69708-X_4

Download citation

  • DOI: https://doi.org/10.1007/3-540-69708-X_4

  • Published:

  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-540-64254-1

  • Online ISBN: 978-3-540-69708-4

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics