Twofold Ferrocene C–H Lithiations For One-Step Difunctionalizations

Abstract

For some aromatics, a twofold C–H deprotolithiation can be achieved, allowing these compounds to be subsequently difunctionalized in one step. This short review brings together examples in which ferrocenes are converted in this way.

1 Introduction

2 Bare Ferrocene

3 Ferrocenes Substituted by Alkyl or Silyl Groups

4 Ferrocenes Substituted by Aminoalkyls

5 Ferrocenes Substituted by Halogens or Oxygen-Based Groups

6 Ferrocenes Substituted by Alkoxyalkyls or Acetals

7 Ferrocenes Substituted by Sulfoxides

8 Ferrocenes Substituted by Oxazolines

9 Ferrocenes Substituted by Carboxamides

10 Conclusion

Key words

ferrocene - deprotolithiation - dilithio compounds - electrophilic trapping - planar chirality - chiral directing group - chiral ligand - ferrocenophane

• References


For access to dilithium compounds using these methodologies, see:
• 1a Maercker A, Theis M. Top. Curr. Chem. 1987; 138: 1
• 1b Foubelo F, Yus M. Trends Org. Chem. 1998; 7: 1
• 1c Foubelo F, Yus M. Curr. Org. Chem. 2005; 9: 459
• 2 Kealy TJ, Pauson PL. Nature (London) 1951; 168: 1039
• 3a Ferrocenes: Homogeneous Catalysis, Organic Synthesis, Materials Science. Togni A, Hayashi T. Wiley-VCH; Weinheim: 2007
• 3b Ferrocenes: Ligands, Materials and Biomolecules . Štěpnička P. John Wiley & Sons; Chichester: 2008
• 3c Astruc D. Eur. J. Inorg. Chem. 2017; 6
• 4a Ferrocenes . Togni A, Hayashi T. VCH; Weinheim: 1995
• 4b Richards CJ, Locke AJ. Tetrahedron: Asymmetry 1998; 9: 2377
• 4c Dai L.-X, Tu T, You S.-L, Deng W.-P, Hou X.-L. Acc. Chem. Res. 2003; 36: 659
• 4d Atkinson RC. J, Gibson VC, Long NJ. Chem. Soc. Rev. 2004; 33: 313
• 4e Gómez-Arrayás R, Adrio J, Carretero JC. Angew. Chem. Int. Ed. 2006; 45: 7674
• 4f Miyake Y, Nishibayashi Y, Uemura S. Synlett 2008; 1747
• 4g Chiral Ferrocenes in Asymmetric Catalysis . Dai L.-X, Hou X.-L. Wiley; New York: 2010
• 4h Noël T, Van der Eycken J. Green Process. Synth. 2013; 2: 297
• 4i Butt NA, Liu D, Zhang W. Synlett 2014; 25: 615
• 4j Drusan M, Šebesta R. Tetrahedron 2014; 70: 759
• 5 Synthetic Metal-Containing Polymers . Manners I. Wiley-VCH; Weinheim: 2004
• 6 Patra M, Gasser G. Nat. Rev. Chem. 2017; 1: 0066

For reviews on ferrocene functionalization including ferrocene deprotometalation, see:
• 7a Kagan HB, Diter P, Gref A, Guillaneux D, Masson-Szymczak A, Rebière F, Riant O, Samuel O, Taudien S. Pure Appl. Chem. 1996; 68: 29
• 7b Balavoine GG. A, Daran JC, Iftime G, Manoury E, Moreau-Bossuet C. J. Organomet. Chem. 1998; 567: 191
• 7c Butler IR. Eur. J. Inorg. Chem. 2012; 4387
• 7d Schaarschmidt D, Lang H. Organometallics 2013; 32: 5668
• 7e Dwadnia N, Roger J, Pirio N, Cattey H, Hierso J.-C. Coord. Chem. Rev. 2018; 355: 74
• 8 Slocum DW, Engelmann TR, Ernst CR, Jennings CA, Jones WE. III, Koonsvitsky BP, Lewis JJ, Shenkin PS. J. Chem. Educ. 1969; 46: 144
• 9 Slocum DW, Rockett BW, Hauser CR. J. Am. Chem. Soc. 1965; 87: 1241
• 10 Rausch M, Vogel M, Rosenberg H. J. Org. Chem. 1957; 22: 900
• 11 Sasamori T, Suzuki Y, Tokitoh N. Organometallics 2014; 33: 6696
• 12 Guillaneux D, Kagan HB. J. Org. Chem. 1995; 60: 2502
• 13 Sanders R, Mueller-Westerhoff UT. J. Organomet. Chem. 1996; 512: 219
• 14 Eberhardt GG, Butte WA. J. Org. Chem. 1964; 29: 2928
• 15 Rausch MD, Ciappenelli D. J. Organomet. Chem. 1967; 10: 127
• 16a Mueller-Westerhoff UT, Yang Z, Ingram G. J. Organomet. Chem. 1993; 463: 163
• 16b Glidewell C, Royles BJ. L, Smith DM. J. Organomet. Chem. 1997; 527: 259
• 16c Khobragade DA, Mahamulkar SG, Pospisil L, Cisarova I, Rulisek L, Jahn U. Chem. Eur. J. 2012; 18: 12267
• 16d Kovar RF, Rausch MD, Rosenberg H. Organomet. Chem. Synth. 1971; 1: 173
• 16e Inkpen MS, Du S, Hildebrand M, White AJ. P, Harrison NM, Albrecht T, Long NJ. Organometallics 2015; 34: 5461
• 16f Inkpen MS, Du S, Driver M, Albrecht T, Long NJ. Dalton Trans. 2013; 42: 2813
• 16g Roemer M, Nijhuis CA. Dalton Trans. 2014; 43: 11815
• 16h Bulfield D, Maschke M, Lieb M, Metzler-Nolte N. J. Organomet. Chem. 2015; 797: 125
• 16i Herberhold M, Dörfler U, Wrackmeyer B. J. Organomet. Chem. 1997; 530: 117
• 16j Brown RA, Houlton A, Roberts RM. G, Silver J, Frampton CS. Polyhedron 1992; 11: 2611
• 16k Cerveau G, Chuit C, Colomer E, Corriu RJ. P, Reye C. Organometallics 1990; 9: 2415
• 16l Calhorda MJ, Lopes PE. M, Schier A, Herrmann R. J. Organomet. Chem. 1997; 543: 93
• 16m Wrighton MS, Palazzotto MC, Bocarsly AB, Bolts JM, Fischer AB, Nadjo L. J. Am. Chem. Soc. 1978; 100: 7264
• 16n Cullen WR, Kim TJ, Einstein FW. B, Jones T. Organometallics 1983; 2: 714
• 16o Butler IR, Cullen WR, Kim TJ, Rettig SJ, Trotter J. Organometallics 1985; 4: 972
• 16p Punji B, Mague JT, Balakrishna MS. Inorg. Chem. 2007; 46: 10268
• 16q Gawron M, Dietz C, Lutter M, Duthie A, Jouikov V, Jurkschat K. Chem. Eur. J. 2015; 21: 16609
• 16r McCulloch B, Ward DL, Woollins JD, Brubaker CH. Jr. Organometallics 1985; 4: 1425
• 16s Bishop JJ, Davison A, Katcher ML, Lichtenberg DW, Merrill RE, Smart JC. J. Organomet. Chem. 1971; 27: 241
• 17a Nguyen P, Stojcevic G, Kulbaba K, MacLachlan MJ, Liu X.-H, Lough AJ, Manners I. Macromolecules 1998; 31: 5977
• 17b Osborne AG, Whiteley RH, Meads RE. J. Organomet. Chem. 1980; 193: 345
• 17c Osborne AG, Whiteley RH. J. Organomet. Chem. 1975; 101: C27
• 17d Fischer AB, Kinney JB, Staley RH, Wrighton MS. J. Am. Chem. Soc. 1979; 101: 6501
• 17e MacLachlan MJ, Lough AJ, Geiger WE, Manners I. Organometallics 1998; 17: 1873
• 17f Foucher D, Ziembinski R, Petersen R, Pudelski J, Edwards M, Ni Y, Massey J, Jaeger CR, Vancso GJ, Manners I. Macromolecules 1994; 27: 3992
• 17g Pudelski JK, Rulkens R, Foucher DA, Lough AJ, MacDonald PM, Manners I. Macromolecules 1995; 28: 7301
• 17h Seyferth D, Withers HP. Jr. Organometallics 1982; 1: 1275
• 17i Butler IR, Cullen WR, Einstein FW. B, Rettig SJ, Willis AJ. Organometallics 1983; 2: 128
• 17j Brunner H, Klankermayer J, Zabel M. J. Organomet. Chem. 2000; 601: 211
• 17k Herberhold M, Hertel F, Milius W, Wrackmeyer B. J. Organomet. Chem. 1999; 582: 352
• 17l Rulkens R, Gates DP, Balaishis D, Pudelski JK, McIntosh DF, Lough AJ, Manners I. J. Am. Chem. Soc. 1997; 119: 10976
• 17m Pudelski JK, Gates DP, Rulkens R, Lough AJ, Manners I. Angew. Chem., Int. Ed. Engl. 1995; 34: 1506
• 17n Foucher DA, Edwards M, Burrow RA, Lough AJ, Manners I. Organometallics 1994; 13: 4959
• 17o Blake AJ, Mayers FR, Osborne AG, Rosseinsky DR. J. Chem. Soc., Dalton Trans. 1982; 2379
• 17p Osborne AG, Hollands RE, Howard JA. K, Bryan RF. J. Organomet. Chem. 1981; 205: 395
• 17q Berenbaum A, Braunschweig H, Dirk R, Englert U, Green JC, Jäkle F, Lough AJ, Manners I. J. Am. Chem. Soc. 2000; 122: 5765
• 17r Braunschweig H, Dirk R, Muller M, Nguyen P, Resendes R, Gates DP, Manners I. Angew. Chem., Int. Ed. Engl. 1997; 36: 2338
• 18a Herbert DE, Mayer UF. J, Manners I. Angew. Chem. Int. Ed. 2007; 46: 5060
• 18b Perucha AS, Heilmann-Brohl J, Bolte M, Lerner H.-W, Wagner M. Organometallics 2008; 27: 6170
• 18c Braunschweig H, Kupfer T. Eur. J. Inorg. Chem. 2012; 1319
• 18d Musgrave RA, Russell AD, Manners I. Organometallics 2013; 32: 5654
• 19 Matas I, Whittell GR, Partridge BM, Holland JP, Haddow MF, Green JC, Manners I. J. Am. Chem. Soc. 2010; 132: 13279
• 20a Carroll MA, Widdowson DA, Williams DJ. Synlett 1994; 1025
• 20b Balavoine GG. A, Doisneau G, Fillebeen-Khan T. J. Organomet. Chem. 1991; 412: 381
• 20c Zhang W, Yoneda Y.-I, Kida T, Nakatsuji Y, Ikeda I. J. Organomet. Chem. 1999; 574: 19
• 20d Jautze S, Seiler P, Peters R. Chem. Eur. J. 2008; 14: 1430
• 20e Otón F, Espinosa A, Tárraga A, Ramírez de Arellano C, Molina P. Chem. Eur. J. 2007; 13: 5742
• 20f Dong T.-Y, Lai L.-L. J. Organomet. Chem. 1996; 509: 131
• 20g Knapp R, Rehahn M. J. Organomet. Chem. 1993; 452: 235
• 20h Schachner JA, Lund CL, Quail JW, Mueller J. Organometallics 2005; 24: 785
• 20i Lund CL, Schachner JA, Quail JW, Mueller J. Organometallics 2006; 25: 5817
• 20j Honeychuck RV, Okoroafor MO, Shen LH, Brubaker CH. Jr. Organometallics 1986; 5: 482
• 20k Schachner JA, Lund CL, Quail JW, Mueller J. Organometallics 2005; 24: 4483
• 20l Wright ME. Organometallics 1990; 9: 853
• 20m Jäkle F, Rulkens R, Zech G, Foucher DA, Lough AJ, Manners I. Chem. Eur. J. 1998; 4: 2117
• 20n Rulkens R, Lough AJ, Manners I. Angew. Chem., Int. Ed. Engl. 1996; 35: 1805
• 21 Walczak M, Walczak K, Mink R, Rausch MD, Stucky G. J. Am. Chem. Soc. 1978; 100: 6382
• 22a Butler IR, Cullen WR, Ni J, Rettig SJ. Organometallics 1985; 4: 2196
• 22b Sänger I, Heilmann JB, Bolte M, Lerner H.-W, Wagner M. Chem. Commun. 2006; 2027
• 23 Masson G, Beyer P, Cyr PW, Lough AJ, Manners I. Macromolecules 2006; 39: 3720
• 24 Benkeser RA, Bach JL. J. Am. Chem. Soc. 1964; 86: 890
• 25 Pudelski JK, Foucher DA, Honeyman CH, Lough AJ, Manners I, Barlow S, O’Hare D. Organometallics 1995; 14: 2470
• 26 Reetz MT, Beuttenmüller EW, Goddard R, Pastó M. Tetrahedron Lett. 1999; 40: 4977
• 27a Aratani T, Gonda T, Nozaki H. Tetrahedron Lett. 1969; 10: 2265
• 27b Aratani T, Gonda T, Nozaki H. Tetrahedron 1970; 26: 5453
• 28 Davison A, Smart JC. J. Organomet. Chem. 1969; 19: P7
• 29 Compton DL, Rauchfuss TB. Organometallics 1994; 13: 4367
• 30 Brandt PF, Compton DL, Rauchfuss TB. Organometallics 1998; 17: 2702
• 31 Hillman M, Matyevich L, Fujita E, Jagwani U, McGowan J. Organometallics 1982; 1: 1226
• 32 Masson G, Lough AJ, Manners I. Macromolecules 2008; 41: 539
• 33a Petrov AR, Derheim A, Oetzel J, Leibold M, Bruhn C, Scheerer S, Oßwald S, Winter RF, Siemeling U. Inorg. Chem. 2015; 54: 6657

For a synthesis of the dibromo product, see also:
• 33b Lerayer E, Renaut P, Roger J, Pirio N, Cattey H, Devillers CH, Lucas D, Hierso J.-C. Chem. Commun. 2017; 53: 6017 ; and references therein
• 34 Roemer M, Heinrich D, Kang YK, Chung YK, Lentz D. Organometallics 2012; 31: 1500
• 35 Butler IR, Cullen WR. Organometallics 1986; 5: 2537
• 36 Peckham TJ, Foucher DA, Lough AJ, Manners I. Can. J. Chem. 1995; 73: 2069
• 37 Artemova NV, Chevykalova MN, Luzikov YN, Nifant’ev IE, Nifant’ev EE. Tetrahedron 2004; 60: 10365
• 38 Hayashi T, Mise T, Fukushima M, Kagotani M, Nagashima N, Hamada Y, Matsumoto A, Kawakami S, Konishi M, Yamamoto K, Kumada M. Bull. Chem. Soc. Jpn. 1980; 53: 1138
• 39 Manzano BR, Jalón FA, Gómez-de la Torre F, López-Agenjo AM, Rodríguez AM, Mereiter K, Weissensteiner W, Sturm T. Organometallics 2002; 21: 789

See also:
• 40a Ito Y, Sawamura M, Hayashi T. J. Am. Chem. Soc. 1986; 108: 6405
• 40b Hayashi T. Pure Appl. Chem. 1988; 60: 7
• 40c Hayashi T, Yamamoto A, Hojo M, Ito Y. J. Chem. Soc., Chem. Commun. 1989; 495
• 40d Hayashi T, Yamamoto A, Hojo M, Kishi K, Ito Y, Nishioka E, Miura H, Yanagai K. J. Organomet. Chem. 1989; 370: 129
• 41 Butler IR, Cullen WR, Rettig SJ. Can. J. Chem. 1987; 65: 1452
• 42 Hayashi T, Yamazaki A. J. Organomet. Chem. 1991; 413: 295
• 43 Hayashi T, Yamamoto K, Kumada M. Tetrahedron Lett. 1974; 15: 4405
• 44 Fukuzawa S.-i, Wachi D. Heteroat. Chem. 2006; 17: 118
• 45 Butler IR, Cullen WR, Rettig SJ. Organometallics 1986; 5: 1320
• 46 Khozeimeh Sarbisheh E, Esteban Flores J, Anderson BJ, Zhu J, Müller J. Organometallics 2017; 36: 2182
• 47 Pastor SD, Togni A. J. Am. Chem. Soc. 1989; 111: 2333
• 48 Slocum DW, Jennings CA, Engelmann TR, Rockett BW, Hauser CR. J. Org. Chem. 1971; 36: 377
• 49 Kutschera G, Kratky C, Weissensteiner W, Widhalm M. J. Organomet. Chem. 1996; 508: 195
• 50 Song J.-H, Cho D.-J, Jeon S.-J, Kim Y.-H, Kim T.-J, Jeong JH. Inorg. Chem. 1999; 38: 893
• 51 Fukuzawa S.-I, Yamamoto M, Hosaka M, Kikuchi S. Eur. J. Org. Chem. 2007; 5540
• 52a Schwink L, Knochel P. Tetrahedron Lett. 1996; 37: 25
• 52b Schwink L, Knochel P. Chem.–Eur. J. 1998; 4: 950
• 52c Perea JJ. A, Borner A, Knochel P. Tetrahedron Lett. 1998; 39: 8073
• 52d Perea JJ. A, Lotz M, Knochel P. Tetrahedron: Asymmetry 1999; 10: 375
• 53 Kang J, Lee JH, Ahn SH, Choi JS. Tetrahedron Lett. 1998; 39: 5523
• 54 Kang J, Yew KH, Kim TH, Choi DH. Tetrahedron Lett. 2002; 43: 9509
• 55 Voituriez A, Panossian A, Fleury-Brégeot N, Retailleau P, Marinetti A. Adv. Synth. Catal. 2009; 351: 1968
• 56 Voituriez A, Panossian A, Fleury-Brégeot N, Retailleau P, Marinetti A. J. Am. Chem. Soc. 2008; 130: 14030
• 57 Neel M, Panossian A, Voituriez A, Marinetti A. J. Organomet. Chem. 2012; 716: 187
• 58 Ganter C, Wagner T. Chem. Ber. 1995; 128: 1157
• 59 Allouch F, Dwadnia N, Vologdin NV, Svyaschenko YV, Cattey H, Penouilh M.-J, Roger J, Naoufal D, Ben Salem R, Pirio N, Hierso J.-C. Organometallics 2015; 34: 5015
• 60 Bernhartzeder S, Kempinger W, Sünkel K. J. Organomet. Chem. 2014; 752: 147
• 61 Long NJ, Martin J, White AJ. P, Williams DJ. J. Chem. Soc., Dalton Trans. 1997; 3083
• 62 Bushell K, Gialou C, Goh CH, Long NJ, Martin J, White AJ. P, Williams CK, Williams DJ, Fontani M, Zanello P. J. Organomet. Chem. 2001; 637–639: 418
• 63 Schaarschmidt D, Lang H. Eur. J. Inorg. Chem. 2010; 4811
• 64 Li H, Cheng H.-S, Seow A.-H, Loh T.-P. Tetrahedron Lett. 2007; 48: 2209
• 65 Carroll MA, White AJ. P, Widdowson DA, Williams DJ. J. Chem. Soc., Perkin Trans. 1 2000; 1551
• 66 Petter RC, Milberg CI. Tetrahedron Lett. 1989; 30: 5085
• 67 Iftime G, Daran J.-C, Manoury E, Balavoine GG. A. Angew. Chem. Int. Ed. 1998; 37: 1698
• 68 Iftime G, Daran J.-C, Manoury E, Balavoine GG. A. J. Organomet. Chem. 1998; 565: 115
• 69 Connell A, Holliman PJ, Butler IR, Male L, Coles SJ, Horton PN, Hursthouse MB, Clegg W, Russo L. J. Organomet. Chem. 2009; 694: 2020
• 70 Hildebrandt A, Al Khalyfeh K, Schaarschmidt D, Korb M. J. Organomet. Chem. 2016; 804: 87
• 71 Rebière F, Riant O, Ricard L, Kagan HB. Angew. Chem., Int. Ed. Engl. 1993; 32: 568
• 72 Raghunath M, Gao W, Zhang X. Tetrahedron: Asymmetry 2005; 16: 3676
• 73 Sutcliffe OB, Bryce MR. Tetrahedron: Asymmetry 2003; 14: 2297
• 74 Wu H, An Q, Liu D, Zhang W. Tetrahedron 2015; 71: 5112 ; and references cited therein
• 75 Park J, Lee S, Ahn KH, Cho C.-W. Tetrahedron Lett. 1995; 36: 7263
• 76a Zhang W, Adachi Y, Hirao T, Ikeda I. Tetrahedron: Asymmetry 1996; 7: 451
• 76b Cho Y.-J, Carroll MA, White AJ. P, Widdowson DA, Williams DJ. Tetrahedron Lett. 1999; 40: 8265
• 77 Park J, Lee S, Ahn KH, Cho C.-W. Tetrahedron Lett. 1996; 37: 6137
• 78 Laufer RS, Veith U, Taylor NJ, Snieckus V. Org. Lett. 2000; 2: 629
• 79 Zhang W, Adachi Y, Hirao T, Ikeda I. Tetrahedron: Asymmetry 1996; 7: 1235
• 80 Lee S, Koh JH, Park J. J. Organomet. Chem. 2001; 637–639: 99
• 81a Zhang W, Yoshinaga H, Imai Y, Kida T, Nakatsuji Y, Ikeda I. Synlett 2000; 1512
• 81b Bolm C, Hermanns N, Kesselgruber M, Hildebrand JP. J. Organomet. Chem. 2001; 624: 157
• 82 Locke AJ, Pickett TE, Richards CJ. Synlett 2001; 141
• 83 Arthurs RA, Richards CJ. Synlett 2018; 29: 585
• 84a Kim S.-G, Cho C.-W, Ahn KH. Tetrahedron: Asymmetry 1997; 8: 1023
• 84b Kim S.-G, Cho C.-W, Ahn KH. Tetrahedron 1999; 55: 10079
• 85 Jendralla H, Paulus E. Synlett 1997; 471
• 86 Miao B, Tinkl M, Snieckus V. Tetrahedron Lett. 1999; 40: 2449
• 87 Laufer R, Veith U, Taylor NJ, Snieckus V. Can. J. Chem. 2006; 84: 356
• 88 Philipova I, Stavrakov G, Chimov A, Nikolova R, Shivachev B, Dimitrov V. Tetrahedron: Asymmetry 2011; 22: 970
• 89a Clegg W, Henderson KW, Kennedy AR, Mulvey RE, O’Hara CT, Rowlings RB, Tooke DM. Angew. Chem. Int. Ed. 2001; 40: 3902
• 89b Henderson KW, Kennedy AR, Mulvey RE, O’Hara CT, Rowlings RB. Chem. Commun. 2001; 1678
• 89c Andrikopoulos PC, Armstrong DR, Clegg W, Gilfillan CJ, Hevia E, Kennedy AR, Mulvey RE, O’Hara CT, Parkinson JA, Tooke DM. J. Am. Chem. Soc. 2004; 126: 11612
• 90a García-Álvarez J, Kennedy AR, Klett J, Mulvey RE. Angew. Chem. Int. Ed. 2007; 46: 1105
• 90b Blair VL, Carrella LM, Clegg W, Klett J, Mulvey RE, Rentschler E, Russo L. Chem. Eur. J. 2009; 15: 856
• 91 Clegg W, Crosbie E, Dale-Black SH, Hevia E, Honeyman GW, Kennedy AR, Mulvey RE, Ramsay DL, Robertson SD. Organometallics 2015; 34: 2580
• 92 Dayaker G, Sreeshailam A, Chevallier F, Roisnel T, Radha Krishna P, Mongin F. Chem. Commun. 2010; 46: 2862