Development of Noncovalent Supported Ionic Liquid Phase Catalyst (SILPC) for Liquid-Phase Reaction as a Benign and Sustainable Protocol to Immobilize Homogeneous Catalyst

Abstract

Homogeneous catalysts were immobilized to the pores of amorphous inorganic supports with the aid of an ionic liquid as Pd-, Cu-, and Ru-supported ionic liquid phase catalyst (SILPC), which is a benign method to immobilize sophisticated but unstable homogeneous catalysts so far difficult to load in an inorganic support by simple impregnation method. By immobilizing as a SILPC, sustainability and reactivity of catalysts increased in Mizoroki–Heck reaction, Suzuki–Miyaura reaction, Huisgen [3+2] cycloaddition (click reaction) without external ligand in aqueous media and ambient atmosphere, and olefin metathesis reactions. In addition, palladium was immobilized on nano-silica gel dendrimer as a nano-SILPC, which was highly active to Suzuki–Miyaura reaction. Moreover, MacMillan imidazolidinone organomolecular catalyst was immobilized as a Mac-SILPC to enable sustainable asymmetric Diels–Alder reaction. SILPCs could be repeatedly used by filtration.

1 Introduction

2 Recyclable Mizoroki–Heck Reaction in an Ionic Liquid Catalyzed­ by Pd/C

3 Immobilization of Pd in an Amorphous Inorganic Oxide with the Aid of an Ionic Liquid – Preparation of Pd-SILPC

4 Mizoroki–Heck Reaction Catalyzed by Pd-SILPC

5 Mizoroki–Heck Reaction in Water Catalyzed by Pd-SILPC

6 Suzuki–Miyaura Reaction Catalyzed by Pd-SILPC

7 Immobilization of Pd in Nano-Silica Gel Dendrimer as Pd-Nano-SILPC and Suzuki–Miyaura Reaction

8 Polymer-Coated Pd-SILPC and Suzuki–Miyaura Reaction

9 Catalytic Hydrogenation Catalyzed by Pd-SH-SILPC

10 Immobilization of Cu as Cu-SILPC and Huisgen [3+2] Cycloaddition­

11 Immobilization of Grubbs Catalyst as Ru-SILPC and Olefin Metathesis Reaction

12 Immobilization of MacMillan Organocatalyst as Mac-SILPC and Asymmetric Diels–Alder Reaction

13 Conclusions

Key words

ionic liquids - heterogeneous catalysis - catalyst immobilization - SILPC - supported catalysis

• References

• 1a Ionic Liquids in Organic Synthesis. Malhotra SV. ACS Symposium Series 950, ACS; Washington D. C.: 2007
• 1b Ionic Liquids in Synthesis. Wasserscheid P. Welton T.; Wiley-VCH; Weinheim: 2008
• 1c Green Industrial Applications of Ionic Liquids. Rogers RD, Seddon KR. Kluwer; Dordrecht: 2003
• 1d Olivier-Bourbigou H, Magna L. J. Mol. Catal. A: Chem 2002; 182-183: 419
• 1e Dupont J, de Souza RF, Suarez PA. Z. Chem. Rev. 2002; 102: 3667
• 1f Ionic Liquids: Industrial Applications to Green Chemistry. Rogers RD, Seddon KR. ACS Symposium Series 818, ACS; Washington D. C.: 2002
• 1g Welton T. Chem. Rev. 1999; 99: 2071
• 2a Beletskaya IP, Cheprakov AV. Chem. Rev. 2000; 100: 3009
• 2b Whitcombe NJ, Hii KK, Gibson SE. Tetrahedron 2001; 57: 7449
• 3 Hagiwara H, Shimizu Y, Hoshi T, Suzuki T, Ando M, Ohkubo K, Yokoyama C. Tetrahedron Lett. 2001; 42: 4349
• 4 Hagiwara H, Sugawara Y, Isobe K, Hoshi T, Suzuki T. Org. Lett. 2004; 6: 2325
• 5a Gozzo FC, Santos LS, Augusti R, Consorti CS, Dupont J, Eberlin MN. Chem. Eur. J. 2004; 10: 6187
• 5b Lungwitz R, Spange S. J. Phys. Chem. C. 2008; 112: 19443
• 6 Muldoon MJ, Gordon CM, Dunkin IR. J. Chem. Soc., Perkin Trans. 2 2001; 433

• Recent representative advances on SILPC:

• 7a Mehnert CP, Mozeleski EJ, Cook RA. Chem. Commun. 2002; 3010
• 7b Mehnert CP, Raymond AC, Dispenziere NC, Afeworki MJ. J. Am. Chem. Soc. 2002; 124: 12932
• 7c Riisager A, Wasserscheid P, van Hal R, Fehrmann R. J. Catal. 2003; 219: 452
• 7d Huang J, Jiang T, Gao H, Han B, Liu Z, Wu W, Chang Y, Zhao G. Angew. Chem. Int. Ed. 2004; 43: 1397
• 7e Breitenlechner S, Fleck M, Müller TE, Suppan A. J. Mol. Catal. A: Chem. 2004; 214: 175
• 7f Riisager A, Fehrmann R, Flicker S, van Hal R, Hanmann M, Wasserscheid P. Angew. Chem. Int. Ed. 2005; 44: 815
• 7g Mehnert CP. Chem. Eur. J. 2005; 11: 50
• 7h Lou L.-L, Yu K, Ding F, Thou W, Peng X, Liu S. Tetrahedron Lett. 2006; 47: 6513
• 7i Gu Y, Li G. Adv. Synth. Catal. 2009; 351: 817
• 7j Zhang Q, Zhang S, Deng Y. Green Chem. 2011; 2619
• 8a Li C.-J. Chem. Rev. 1993; 93: 2023
• 8b Lubenau A, Auge J, Queneau Y. Synthesis 1994; 741
• 8c Organic Reactions in Aqueous Media. Li C.-J, Chan T.-H. Wiley; New York: 1997
• 8d Organic Synthesis in Water. Grieco PA. Blake Academic and Professional; London: 1998
• 8e Ribe S, Wipf P. Chem. Commun. 2001; 299
• 8f Lindström UM. Chem. Rev. 2002; 102: 2751
• 8g Kobayashi S, Manabe K. Acc. Chem. Res. 2002; 35: 209
• 8h Kobayashi S, Manabe K. Chem. Eur. J. 2002; 8: 4094
• 8i Li C.-J. Chem. Rev. 2005; 105: 3095
• 8j Li C.-J, Chan T.-H. Organic Reactions in Aqueous Media. 2nd ed. Wiley; Hoboken, NJ: 2007
• 8k Organic Reactions in Water . Lindström UM. Blackwell; Oxford: 2007
• 8l Minakata S, Komatsu M. Chem. Rev. 2009; 109: 711
• 9 Hagiwara H, Sugawara Y, Hoshi T, Suzuki T. Chem. Commun. 2005; 2942
• 10a de Vries AH. M, Mulders JM. C. A, Mommers JH. M, Henderickx HJ. W, de Vries JG. Org. Lett. 2003; 5: 3285
• 10b Reetz MT, de Vries JG. Chem. Commun. 2004; 1559

• For recent reviews on Suzuki–Miyaura reaction, see:

• 11a Miyaura N, Suzuki A. Chem. Rev. 1995; 95: 2457
• 11b Littke AF, Fu GC. Angew. Chem. Int. Ed. 2002; 41: 4176
• 11c Miyaura N. Top. Curr. Chem. 2002; 219: 11
• 11d Hassan J, Sevignon M, Gozzi C, Schulz E, Lemaire M. Chem. Rev. 2002; 102: 1359
• 11e Kotha S, Lahiri K, Kashinath D. Tetrahedron 2002; 58: 9633
• 11f Bellina F, Carpita A, Rossi R. Synthesis 2004; 2419
• 11g Alonso F, Beletskaya IP, Yus M. Tetrahedron 2008; 64: 3047
• 11h Martin R, Buchwald SL. Acc. Chem. Res. 2008; 41: 1461
• 12 Rouhi AM. Chem. Eng. News 2004; 82: 49

• For recent representative examples of ligandless Suzuki–Miyaura reaction catalyzed by heterogeneous catalyst on a solid support, see:

• 13a Kudo D, Masui Y, Onaka M. Chem. Lett. 2007; 36: 918
• 13b Kazmaier U, Hähn S, Weiss TD, Kautenburger R, Maier WF. Synlett 2007; 2579
• 13c Artok L, Bulut H. Tetrahedron Lett. 2004; 45: 3881
• 13d Daku KM. L, Newton RF, Pearce SP, Vileb J, William JM. J. Tetrahedron Lett. 2003; 44: 5095
• 14 Hagiwara H, Ko KH, Hoshi T, Suzuki T. Chem. Commun. 2007; 2838

• Some selected Suzuki–Miyaura reactions in aqueous alcohol:

• 15a Marck G, Villiger A, Buchecker R. Tetrahedron Lett. 1994; 35: 3277
• 15b Liu L, Zhang Y, Xin BJ. J. Org. Chem. 2006; 71: 3994
• 15c Zhang G. Synthesis 2005; 537
• 15d Arvela RK, Leadbeater NE, Collins MJ. Jr. Tetrahedron 2005; 61: 9349
• 15e Chanthavong F, Leadbeater NE. Tetrahedron Lett. 2006; 47: 1909
• 15f Hagiwara H, Ko KH, Hoshi T, Suzuki T. Synlett 2008; 618
• 16a Tsubokawa N, Ichioka H, Saitoh T, Fujiki K. React. Funct. Polym. 1998; 37: 75
• 16b Murota M, Sato S, Tsubokawa N. Polym. Adv. Technol. 2002; 13: 144
• 17 Hagiwara H, Sasaki H, Tsubokawa N, Hoshi T, Suzuki T, Tsuda T, Kuwabata S. Synlett 2010; 1990
• 18 Hagiwara H, Sato K, Hoshi T, Suzuki T. Synlett 2011; 2545
• 19 Hagiwara H, Nakamura T, Hoshi T, Suzuki T. Green Chem. 2011; 13: 1133
• 20 Ho T.-L. Hard and Soft Acids and Bases Principle in Organic Chemistry. Academic Press; New York: 1977
• 21 Berger A, de Souza RF, Delgado MR, Dupont J. Tetrahedron: Asymmetry 2001; 12: 1825

• Some representative reviews:

• 22a Kolb HC, Finn MG, Sharpless KB. Angew. Chem. Int. Ed. 2001; 40: 2004
• 22b Bock VD, Hiemstra H, van Maarseveen J. Eur. J. Org. Chem. 2006; 51
• 22c Meldal M, Tornøe CW. Chem. Rev. 2008; 108: 2952
• 22d Lutz J.-F. Angew. Chem. Int. Ed. 2007; 46: 1018
• 22e Malkoch M, Schleicher K, Drockenmuller E, Hawker CJ, Russell YP, Wu P, Fokin VV. Macromolecules 2005; 38: 3663
• 22f Kolb HC, Sharpless KB. Drug Discov. Today 2003; 8: 1128
• 22g Loaiza PR, Löber S, Hübner H, Gmeiner P. J. Comb. Chem. 2006; 8: 252
• 23a Candelon N, Lastécouères D, Diallo AK, Aranzaes JR, Astruc D, Vincent J.-M. Chem. Commun. 2008; 741
• 23b Bergbreiter DE, Hamilton PN, Koshti NM. J. Am. Chem. Soc. 2007; 129: 10666
• 23c Zhao Y.-B, Yan Z.-Y, Liang Y.-Y. Tetrahedron Lett. 2006; 47: 1545
• 23d Girard C, Önen E, Aufort M, Beauvière S, Samson E, Herscovici J. Org. Lett. 2006; 8: 1689
• 23e Chassaing S, Kumarraja M, Sido AS. S, Pale P, Sommer J. Org. Lett. 2007; 9: 883
• 23f Lipshutz BH, Taft BR. Angew. Chem. Int. Ed. 2006; 45: 8235
• 24 Hagiwara H, Sasaki H, Hoshi T, Suzuki T. Synlett 2009; 643

• Some recent representative reviews:

• 25a Yet L. Chem. Rev. 2000; 100: 2963
• 25b Trnka TM, Grubbs RH. Acc. Chem. Res. 2001; 34: 18
• 25c Grubbs RH. Tetrahedron 2004; 60: 7117
• 25d Schrock RR. Angew. Chem. Int. Ed. 2005; 45: 3748
• 25e Chauvin Y. Angew. Chem. Int. Ed. 2005; 45: 3741
• 25f Grubbs RH. Angew. Chem. Int. Ed. 2005; 45: 3760
• 25g Chattopadhyay SK, Karmakar S, Biswas T, Majumdar KC, Rahamanand H, Roy B. Tetrahedron 2007; 63: 3919
• 25h Clavier H, Grela K, Kirschning A, Mauduit M, Nolan SP. Angew. Chem. Int. Ed. 2007; 46: 6786
• 26a Buijsman RC, van Vuuren E, Sterrenburg JG. Org. Lett. 2001; 3: 3785
• 26b Sémeril D, Olivier-Bourbigou H, Bruneau C, Dixneuf PH. Chem. Commun. 2002; 146
• 26c Miller AL. II, Bowden NB. Chem. Commun. 2007; 2051
• 27 Gibson SE, Swamy VM. Adv. Synth. Catal. 2002; 344: 619
• 28 Mwangi MT, Runge MB, Bowden NB. J. Am. Chem. Soc. 2006; 128: 14434
• 29a Michrowska A, Mennecke K, Kunz U, Kirschning A, Grela K. J. Am. Chem. Soc. 2006; 128: 13261
• 29b Kirschning A, Gulajski L, Mennecke K, Meyer A, Busch T, Grela K. Synlett 2008; 2692
• 30 Hagiwara H, Okunaka N, Hoshi T, Suzuki T. Synlett 2008; 1813
• 31 Hagiwara H, Nakamura T, Okunaka N, Hoshi T, Suzuki T. Helv. Chim. Acta. 2010; 93: 175
• 32a Dalko PI, Moisan L. Angew. Chem. Int. Ed. 2001; 40: 3726
• 32b List B. Synlett 2001; 1675
• 32c Lygo B, Andrews BI. Acc. Chem. Res. 2004; 37: 518
• 32d Ooi T, Maruoka K. Acc. Chem. Res. 2004; 37: 526
• 32e List B. Acc. Chem. Res. 2004; 37: 548
• 32f Notz W, Tanaka F, Barbas CF. III. Acc. Chem. Res. 2004; 37: 580
• 32g Miller SJ. Acc. Chem. Res. 2004; 37: 601
• 32h Agarwal VK, Winn CL. Acc. Chem. Res. 2004; 37: 611
• 32i Tian S.-K, Chen Y, Hang J, Tang L, Mcdaid P, Deng L. Acc. Chem. Res. 2004; 37: 621
• 32j Dondoni A, Massi A. Angew. Chem. Int. Ed. 2008; 47: 4639
• 33a Ahrendt KA, Borths CJ, MacMillan DW. C. J. Am. Chem. Soc. 2000; 122: 4243
• 33b Northrup AB, MacMillan DW. C. J. Am. Chem. Soc. 2002; 124: 2458
• 33c Jen WS, Wiener J, MacMillan DW. C. J. Am. Chem. Soc. 2000; 122: 9874
• 33d Paras NA, MacMillan DW. C. J. Am. Chem. Soc. 2001; 123: 4370
• 33e Austin JF, MacMillan DW. C. J. Am. Chem. Soc. 2002; 124: 1172
• 33f Huang Y, Walji AM, Larsen CH, MacMillan DW. C. J. Am. Chem. Soc. 2005; 127: 15051
• 33g Lelais G, MacMillan DW. C. Aldrichimica Acta. 2006; 39: 79
• 33h Poisson T. Synlett 2008; 147
• 34 Selkala SA, Tois J, Pihko PM, Koskinen AM. P. Adv. Synth. Catal. 2002; 344: 941
• 35a Benaglia M, Celentano G, Cinquini M, Puglisi A, Cozzi F. Adv. Synth. Catal. 2002; 344: 149
• 35b Puglisi A, Benaglia M, Cinquini M, Cozzi F, Celentano G. Eur. J. Org. Chem. 2004; 567
• 35c Benaglia M. New J. Chem. 2006; 30: 1525
• 36 Selkala SA, Tois J, Pihko PM, Koskinen AM. P. Org. Lett. 2007; 9: 3449
• 37 Park JK, Sreekanth P, Kim BM. Adv. Synth. Catal. 2004; 346: 49
• 38 Hagiwara H, Kuroda T, Hoshi T, Suzuki T. Adv. Synth. Catal. 2010; 352: 909
• 39a Arhancet JP, Davis ME, Merola JS, Hanson BE. Nature (London) 1989; 339: 454
• 39b Acres GJ. K, Bond GC, Cooper BJ, Dawson JA. J. Catal. 1966; 6: 139
• 39c Bhanage BM, Shirai M, Arai M. J. Mol. Catal. A: Chem. 1999; 145: 69