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Synthesis of 1,2-Disubstituted Cyclopentadienes and Their Application

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Metallocenes in Regio- and Stereoselective Synthesis

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 74))

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Abstract

Cyclopentadiene and its substituted congeners have played an important role in organic chemistry since their discovery. Cyclopentadienyl and substituted cyclopentadienyl anions constitute currently a very important class of ligands for transition metal compounds. Cyclopentadienyl ligands in the respective metallocene complexes show usually high chemical inertness and stability. This property makes the metallocenes popular and indispensable catalysts in a plethora of organic transformations. This review focuses on development of synthetic pathways for preparation of selectively 1,2-disubstituted cyclopentadienes and their conversion to a wide variety of metallocenes. Application of 1,2-disubstituted metallocenes in catalytic processes is mentioned as well.

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References

  1. Kraemer G, Spilker A (1896) Ber Dtsch Chem Ges 29:552–561

    CAS  Google Scholar 

  2. Kealy TJ, Pauson PL (1951) Nature 168:1039–1040

    CAS  Google Scholar 

  3. Hartwig J (2010) Organotransition metal chemistry. University Science Books, Herndon, VA

    Google Scholar 

  4. Halterman RL (1992) Chem Rev 92:965–994

    CAS  Google Scholar 

  5. Winterfeldt E (1993) Chem Rev 93:827–843

    CAS  Google Scholar 

  6. Santos CS, Burtoloso ACB (2018) Eur J Org Chem 2018:6350–6354

    CAS  Google Scholar 

  7. Möhring PC, Coville NJ (1994) J Organomet Chem 479:1–29

    Google Scholar 

  8. Möhring PC, Coville NJ (1995) J Mol Cat A Chem 96:181–195

    Google Scholar 

  9. Möhring PC, Coville NJ (2006) Coord Chem Rev 250:18–35

    Google Scholar 

  10. Lin W, Li W, Lu D, Su F, Wen T-B, Zhang H-J (2018) ACS Catal 8:8070–8076

    CAS  Google Scholar 

  11. Erker G (1989) Pure Appl Chem 61:1715–1722

    CAS  Google Scholar 

  12. For a related discussion, see: Jones SB, Petersen JL (1981) Inorg Chem 3:2889–2894

    Google Scholar 

  13. Mas-Roselló J, Herraiz AG, Audic B, Laverny A, Cramer N (2021) Angew Chem Int Ed 60:13198–13224

    Google Scholar 

  14. Frei A (2019) Chem A Eur J 25:7074–7090

    CAS  Google Scholar 

  15. Enders M, Bakre RW (2006) Curr Org Chem 10:937–953

    CAS  Google Scholar 

  16. Xi Z (2005) Top Catal 35:63–71

    CAS  Google Scholar 

  17. Coville NJ, du Plooz KE, Pickl W (1992) Coord Chem Rev 116:1–267

    CAS  Google Scholar 

  18. Lee BY, Moon H, Chung YK (1994) J Am Chem Soc 116:2163–2164

    CAS  Google Scholar 

  19. Buchholz H, Reiser O, de Meijere A (1991) Synlett:20–22

    Google Scholar 

  20. Dalkılıç E, Güney M, Daştan A, Saracoglu N, de Lucchi O, Fabris F (2009) Tetrahedron Lett 50:1989–1991

    Google Scholar 

  21. Dalkiliç E, Daştan A (2015) Tetrahedron 71:1966–1970

    Google Scholar 

  22. Topolovčan N, Panov I, Kotora M (2016) Org Lett 18:3634–3637

    PubMed  Google Scholar 

  23. Kaneda K, Uchiyama T, Fujiwara Y, Imanaka T, Teranishi S (1979) J Org Chem 44:55–63

    CAS  Google Scholar 

  24. Shomo T, Nishiguchi I, Okawa M (1976) Chem Lett:573–576

    Google Scholar 

  25. Mironov VA, Sobolev EV, Elizarova AN (1963) Tetrahedron 19:1939–1958

    CAS  Google Scholar 

  26. McLean S, Haynes P (1965) Tetrahedron 21:2313–2327

    CAS  Google Scholar 

  27. Ohara O, Aso C, Sasaki M, Murayama K (1970) Makromol Chem 137:195–202

    Google Scholar 

  28. Schmitt G, Ózman S (1976) Chem-Z 100:143

    CAS  Google Scholar 

  29. Mengele W, Diebold J, Troll C, Röll W, Brintzinger H-H (1993) Organometallics 12:1931–1935

    CAS  Google Scholar 

  30. Mironov VA, Kostina SN, Elizarova AN (1964) Izv Akad Nauk SSSR Ser Khim:875–884

    Google Scholar 

  31. Hughes RP, Kowalski AS, Lomprey JR, Rheingold AL (1994) Organometallics 13:2691–2695

    CAS  Google Scholar 

  32. Hughes RP, Kowalski AS, Lomprey JR, Neithamer DR (1996) J Org Chem 61:401–404

    CAS  Google Scholar 

  33. Hughes RP, Kowalski AS (1995) Inorg Chim Acta 240:653–656

    CAS  Google Scholar 

  34. Calladine JA, Torres O, Anstey M, Ball GE, Bergman RG, Curley J, Duckett SB, George MW, Gilson AI, Lawes DJ, Perutz RN, Sun X-Z, Vollhardt KPC (2010) Chem Sci 1:622–630

    CAS  Google Scholar 

  35. Suzuki N, Mise T, Yamaguchi Y, Chihara T, Ikegami Y, Ohmori H, Matsumoto A, Wakatsuki Y (1998) J Organomet Chem 560:47–54

    CAS  Google Scholar 

  36. Alder K, Ache H-J (1962) Chem Ber 95:503–510

    CAS  Google Scholar 

  37. McLean S, Haynes P (1964) Tetrahedron Lett:2385–2390

    Google Scholar 

  38. McLean S, Haynes P (1965) Tetrahedron 21:2343–2351

    CAS  Google Scholar 

  39. Gruter GJM, van Beek JAM, Green R, IJpei EG. Cyclopentadiene compounds substituted with branched alkyl groups. US Patent 6,124,488, September 26, 2000

    Google Scholar 

  40. van Beek JAM, Gruter GJM, Green R. Process for cyclopentadienes substitution. EP 0805133 A1, April 28, 1997

    Google Scholar 

  41. Little WF, Koestler RC (1961) J Org Chem 26:3245–3247

    CAS  Google Scholar 

  42. Lv J, Zhang L, Hu S, Cheng J-P, Luo S (2012) Chem A Eur J 18:799–803

    CAS  Google Scholar 

  43. Bříza T, Kvíčala J, Mysík P, Paleta O, Čermák J (2001) Synlett:685–687

    Google Scholar 

  44. Bříza T, Kvíčala J, Paleta O, Čermák J (2002) Tetrahedron 58:3841–3846

    Google Scholar 

  45. Bříza T, Kvíčala J, Paleta O, Čermák J (2002) Tetrahedron 58:3847–3854

    Google Scholar 

  46. Čermák J, Šťastná L, Sýkora J, Císařová I, Kvíčala J (2004) Organometallics 23:2850–2854

    Google Scholar 

  47. Šťastná L, Auerová K, Kvíčala J, Čermák J (2007) J Organomet Chem 692:1974–1982

    Google Scholar 

  48. Steffen A, Hagemeister T, Braun T, Jutzi P, Neumann B, Stammler H-G (2007) Organometallics 26:5289–5294

    CAS  Google Scholar 

  49. Scattebøl L (1962) Chem Ind:2146–2147

    Google Scholar 

  50. Scattebøl L (1967) Tetrahedron 23:1107–1117

    Google Scholar 

  51. Spielmann R, Cramers CA (1972) Chromatographia 5:295–300

    CAS  Google Scholar 

  52. Blenkers J, de Liefde Meijer HJ, Teuben J (1983) Organometallics 2:1483–1484

    CAS  Google Scholar 

  53. Hessen B, Blenkers J, Teuben JH (1989) Organometallics 8:2809–2812

    CAS  Google Scholar 

  54. Allen CFH, Jones JE, VanAllan JA (1946) J Org Chem 11:268–276

    CAS  Google Scholar 

  55. Rio G, Mahmoud C (1969) C R Acad Sci Paris Ser C 268:1960–1963

    CAS  Google Scholar 

  56. Rio G, Mahmoud C (1970) Bull Soc Chim Fr 10:3585–3593

    Google Scholar 

  57. Zhang F, Mu Y, Zhao L, Zhang Y, Bu W, Chen C, Zhai H, Hong H (2000) J Organomet Chem 613:68–76

    CAS  Google Scholar 

  58. Zhang F, Mu Y, Zhang Y, Bu W, Chen C, Zhai H, Hong H (2000) Chin Chem Lett 11:641–644

    CAS  Google Scholar 

  59. Padwa A, Blacklock TJ, Getman D, Hatanaka N, Loza R (1978) J Org Chem 43:1481–1492

    CAS  Google Scholar 

  60. Zimmerman E, Kreil DJ (1982) J Org Chem 47:2060–2075

    CAS  Google Scholar 

  61. Rosenblum M, Howells WG, Banerjee AK, Bennet C (1962) J Am Chem Soc 84:2726–2732

    CAS  Google Scholar 

  62. Mull ES, Sattigeri VJ, Rodriguez AL, Katzenellenbogen JA (2002) Bioorg Med Chem 10:1381–1398

    CAS  PubMed  Google Scholar 

  63. Huang H-C, Reitz DR. Substituted cyclopentadienyl compounds for treatment of inflammation. US Patent 5,418,254, May 23, 1995

    Google Scholar 

  64. Deck PA, McCauley BD, Slebodnick C (2006) J Organomet Chem 691:1973–1983

    CAS  Google Scholar 

  65. Deck PA, Jackson WF, Fronczek FR (1996) Organometallics 15:5287–5291

    CAS  Google Scholar 

  66. Deck PA (2006) Coord Chem Rev 250:1032–1055

    CAS  Google Scholar 

  67. Kawasumi K, Odani T, Takeshi K. Electrolytic solution for secondary batteries, secondary battery, battery pack, electric vehicle, electric power storage system, electric power tool, and electronic device. US Patent Application, US 2020/0161707 A1, May 21, 2020

    Google Scholar 

  68. Davis JH, Sun H-N, Redfield D, Stucky GD (1980) J Magn Reson 37:441–448

    CAS  Google Scholar 

  69. Bursten BE, Callstrom MR, Jolly CA, Paquette LA, Sivik MR, Tucker RS, Eartchow CA (1994) Organometallics 13:127–133

    CAS  Google Scholar 

  70. Cozak D, Gauvin F (1987) Organometallics 6:1912–1917

    CAS  Google Scholar 

  71. Börjesson K, Ćoso D, Gray V, Grossman JC, Guan J, Harris CB, Hertkorn N, Hou Z, Kanai Y, Lee D, Lomont JP, Majumdar A, Meier SK, Moth-Poulsen K, Myrabo RL, Nguyen SC, Segalman RA, Srinivasan V, Tolman VB, Vinokurov N, Vollhardt KPC, Weidman TV (2014) Chem A Eur J 20:15587–15604

    Google Scholar 

  72. Bublitz DE (1964) Can J Chem 42:2381–2384

    CAS  Google Scholar 

  73. Rosenblum M, Woodward RB (1958) J Am Chem Soc 80:5443–5449

    CAS  Google Scholar 

  74. Bublitz DE (1969) J Organomet Chem 16:149–161

    CAS  Google Scholar 

  75. Halasa AF, Tate DP (1970) J Organomet Chem 24:769–773

    CAS  Google Scholar 

  76. Butler IR, Evans DM, Horton PN, Coles SJ, Murphy PJ (2021) Organometallics 40:600–605

    CAS  Google Scholar 

  77. Wu H-P, Ess DH, Lanza S, Weakley TJR, Houk KN, Baldridge KK, Haley MM (2007) Organometallics 26:3957–3968

    CAS  Google Scholar 

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Acknowledgment

The authors would like to thank Dr. Timothée Cadart for his useful comments during the last stages of the manuscript preparation.

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Correspondence to Martin Kotora .

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Topolovčan, N., Kotora, M. (2023). Synthesis of 1,2-Disubstituted Cyclopentadienes and Their Application. In: Hapke, M., Kotora, M. (eds) Metallocenes in Regio- and Stereoselective Synthesis. Topics in Organometallic Chemistry, vol 74. Springer, Cham. https://doi.org/10.1007/3418_2023_106

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