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.
References
Kraemer G, Spilker A (1896) Ber Dtsch Chem Ges 29:552–561
Kealy TJ, Pauson PL (1951) Nature 168:1039–1040
Hartwig J (2010) Organotransition metal chemistry. University Science Books, Herndon, VA
Halterman RL (1992) Chem Rev 92:965–994
Winterfeldt E (1993) Chem Rev 93:827–843
Santos CS, Burtoloso ACB (2018) Eur J Org Chem 2018:6350–6354
Möhring PC, Coville NJ (1994) J Organomet Chem 479:1–29
Möhring PC, Coville NJ (1995) J Mol Cat A Chem 96:181–195
Möhring PC, Coville NJ (2006) Coord Chem Rev 250:18–35
Lin W, Li W, Lu D, Su F, Wen T-B, Zhang H-J (2018) ACS Catal 8:8070–8076
Erker G (1989) Pure Appl Chem 61:1715–1722
For a related discussion, see: Jones SB, Petersen JL (1981) Inorg Chem 3:2889–2894
Mas-Roselló J, Herraiz AG, Audic B, Laverny A, Cramer N (2021) Angew Chem Int Ed 60:13198–13224
Frei A (2019) Chem A Eur J 25:7074–7090
Enders M, Bakre RW (2006) Curr Org Chem 10:937–953
Xi Z (2005) Top Catal 35:63–71
Coville NJ, du Plooz KE, Pickl W (1992) Coord Chem Rev 116:1–267
Lee BY, Moon H, Chung YK (1994) J Am Chem Soc 116:2163–2164
Buchholz H, Reiser O, de Meijere A (1991) Synlett:20–22
Dalkılıç E, Güney M, Daştan A, Saracoglu N, de Lucchi O, Fabris F (2009) Tetrahedron Lett 50:1989–1991
Dalkiliç E, Daştan A (2015) Tetrahedron 71:1966–1970
Topolovčan N, Panov I, Kotora M (2016) Org Lett 18:3634–3637
Kaneda K, Uchiyama T, Fujiwara Y, Imanaka T, Teranishi S (1979) J Org Chem 44:55–63
Shomo T, Nishiguchi I, Okawa M (1976) Chem Lett:573–576
Mironov VA, Sobolev EV, Elizarova AN (1963) Tetrahedron 19:1939–1958
McLean S, Haynes P (1965) Tetrahedron 21:2313–2327
Ohara O, Aso C, Sasaki M, Murayama K (1970) Makromol Chem 137:195–202
Schmitt G, Ózman S (1976) Chem-Z 100:143
Mengele W, Diebold J, Troll C, Röll W, Brintzinger H-H (1993) Organometallics 12:1931–1935
Mironov VA, Kostina SN, Elizarova AN (1964) Izv Akad Nauk SSSR Ser Khim:875–884
Hughes RP, Kowalski AS, Lomprey JR, Rheingold AL (1994) Organometallics 13:2691–2695
Hughes RP, Kowalski AS, Lomprey JR, Neithamer DR (1996) J Org Chem 61:401–404
Hughes RP, Kowalski AS (1995) Inorg Chim Acta 240:653–656
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
Suzuki N, Mise T, Yamaguchi Y, Chihara T, Ikegami Y, Ohmori H, Matsumoto A, Wakatsuki Y (1998) J Organomet Chem 560:47–54
Alder K, Ache H-J (1962) Chem Ber 95:503–510
McLean S, Haynes P (1964) Tetrahedron Lett:2385–2390
McLean S, Haynes P (1965) Tetrahedron 21:2343–2351
Gruter GJM, van Beek JAM, Green R, IJpei EG. Cyclopentadiene compounds substituted with branched alkyl groups. US Patent 6,124,488, September 26, 2000
van Beek JAM, Gruter GJM, Green R. Process for cyclopentadienes substitution. EP 0805133 A1, April 28, 1997
Little WF, Koestler RC (1961) J Org Chem 26:3245–3247
Lv J, Zhang L, Hu S, Cheng J-P, Luo S (2012) Chem A Eur J 18:799–803
Bříza T, Kvíčala J, Mysík P, Paleta O, Čermák J (2001) Synlett:685–687
Bříza T, Kvíčala J, Paleta O, Čermák J (2002) Tetrahedron 58:3841–3846
Bříza T, Kvíčala J, Paleta O, Čermák J (2002) Tetrahedron 58:3847–3854
Čermák J, Šťastná L, Sýkora J, Císařová I, Kvíčala J (2004) Organometallics 23:2850–2854
Šťastná L, Auerová K, Kvíčala J, Čermák J (2007) J Organomet Chem 692:1974–1982
Steffen A, Hagemeister T, Braun T, Jutzi P, Neumann B, Stammler H-G (2007) Organometallics 26:5289–5294
Scattebøl L (1962) Chem Ind:2146–2147
Scattebøl L (1967) Tetrahedron 23:1107–1117
Spielmann R, Cramers CA (1972) Chromatographia 5:295–300
Blenkers J, de Liefde Meijer HJ, Teuben J (1983) Organometallics 2:1483–1484
Hessen B, Blenkers J, Teuben JH (1989) Organometallics 8:2809–2812
Allen CFH, Jones JE, VanAllan JA (1946) J Org Chem 11:268–276
Rio G, Mahmoud C (1969) C R Acad Sci Paris Ser C 268:1960–1963
Rio G, Mahmoud C (1970) Bull Soc Chim Fr 10:3585–3593
Zhang F, Mu Y, Zhao L, Zhang Y, Bu W, Chen C, Zhai H, Hong H (2000) J Organomet Chem 613:68–76
Zhang F, Mu Y, Zhang Y, Bu W, Chen C, Zhai H, Hong H (2000) Chin Chem Lett 11:641–644
Padwa A, Blacklock TJ, Getman D, Hatanaka N, Loza R (1978) J Org Chem 43:1481–1492
Zimmerman E, Kreil DJ (1982) J Org Chem 47:2060–2075
Rosenblum M, Howells WG, Banerjee AK, Bennet C (1962) J Am Chem Soc 84:2726–2732
Mull ES, Sattigeri VJ, Rodriguez AL, Katzenellenbogen JA (2002) Bioorg Med Chem 10:1381–1398
Huang H-C, Reitz DR. Substituted cyclopentadienyl compounds for treatment of inflammation. US Patent 5,418,254, May 23, 1995
Deck PA, McCauley BD, Slebodnick C (2006) J Organomet Chem 691:1973–1983
Deck PA, Jackson WF, Fronczek FR (1996) Organometallics 15:5287–5291
Deck PA (2006) Coord Chem Rev 250:1032–1055
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
Davis JH, Sun H-N, Redfield D, Stucky GD (1980) J Magn Reson 37:441–448
Bursten BE, Callstrom MR, Jolly CA, Paquette LA, Sivik MR, Tucker RS, Eartchow CA (1994) Organometallics 13:127–133
Cozak D, Gauvin F (1987) Organometallics 6:1912–1917
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
Bublitz DE (1964) Can J Chem 42:2381–2384
Rosenblum M, Woodward RB (1958) J Am Chem Soc 80:5443–5449
Bublitz DE (1969) J Organomet Chem 16:149–161
Halasa AF, Tate DP (1970) J Organomet Chem 24:769–773
Butler IR, Evans DM, Horton PN, Coles SJ, Murphy PJ (2021) Organometallics 40:600–605
Wu H-P, Ess DH, Lanza S, Weakley TJR, Houk KN, Baldridge KK, Haley MM (2007) Organometallics 26:3957–3968
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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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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