Abstract
A top priority in the development of new catalytic processes
is the challenging full separation of the catalyst components from
the products. Only extremely small residues of metals or ligands
are often tolerated in the final product, particularly in the case
of active pharmaceutical ingredients; additionally, environmental
and cost considerations urge the development of processes that enable
the separation and reuse of the catalyst. Multiphase homogeneous
catalysis provides technical solutions to these needs, as witnessed
by the rapidly accelerating development of this field. Through the
analysis of recent examples, the creativity in devising technical
solutions for multiphase homogeneous reactions is outlined and the
potential rewards are illustrated.
1 Introduction
2 Catalyst Design
3 Classic Multiphase Homogeneous Procedures
3.1 Thermoregulated Solvent Pairs
3.2 Temperature-Induced Catalyst Phase Transfer in a Liquid-Liquid
Biphasic System
3.3 Quaternary Ammonium Salts in Phase Transfer Catalytic Applications
3.4 Quaternary Ammonium Salts as Metal Nanoparticle Stabilizers
4 Liquid-Liquid Biphasic Catalysis with Ion-Tagged
Catalysts
4.1 Ionic Tags and the ‘Electrosteric’ Activation
of a Catalytic Cycle
4.2 Water-Organic Phase Interface Catalysis, Micelles
and Emulsions
5 Switchable Catalysts in Liquid-Liquid Biphasic Systems
6 Homogeneous Catalysis Followed by Post-Reaction Heterogenization
6.1 One-Phase Homogeneous Reaction Followed by Catalyst Precipitation
with the Aid of an Antisolvent
6.2 Solventless Reactions and Highly Concentrated Organic Phases
7 Multiphase Homogeneous Catalysis and Flow Chemistry
8 Conclusion
Key words
multiphase homogeneous catalysis - ionic liquids - ion-tagged catalysts - catalyst recycling - electrosteric
activation
References
1a
Muldoon MJ.
Dalton Trans.
2010,
39:
337
1b
Hugl H.
Nobis M.
Top. Organomet. Chem.
2008,
23:
1
1c
Multiphase Homogeneous
Catalysis
Cornils B.
Herrmann WA.
Horvarth IT.
Leitner W.
Mecking S.
Olivier-Borbigou H.
Vogt D.
Wiley-VCH;
Weinheim / Germany:
2005.
2a
Kohlpaintner CW.
Fischer RW.
Cornils B.
Appl. Catal.,
A
2001,
221:
219
2b
Cornils B.
Kuntz EG.
J. Organomet.
Chem.
1995,
502:
177
3a
Keim W.
Green Chem.
2003,
5:
105
3b
Keim W.
Angew.
Chem. Int. Ed. Engl.
1990,
29:
235
4a
Faber K.
Industrial
Biotransformations
Wiley-VCH;
Weinheim / Germany:
2006.
4b
Reetz MT.
Wiesenhöfer W.
Franciò G.
Leitner W.
Adv. Synth.
Catal.
2003,
345:
1221
5a
Liu S.
Xiao J.
J.
Mol. Catal. A: Chem.
2007,
270:
1
5b
Recovery and Recycling
in Homogeneous Catalysis
Tooze B.
Cole-Hamilton DJ.
Kluwer;
Dordrecht:
2005.
6a
Shaughnessy KH.
Chem. Rev.
2009,
109:
643
6b
Minakata S.
Komatsu M.
Chem. Rev.
2009,
109:
711
6c
Chanda A.
Fokin VV.
Chem. Rev.
2009,
109:
643
6d
Lindström UM.
Chem. Rev.
2002,
102:
2751
7a
Zhang W.
Green Chem.
2009,
11:
911
7b
Cole-Hamilton DJ.
Adv. Synth. Catal.
2006,
348:
1341
8a
Luo S.
Zhang L.
Cheng J.-P.
Chem. Asian J.
2009,
4:
1184
8b
Šebesta R.
Kmentová I.
Toma Š.
Green Chem.
2008,
10:
484
8c
de María PD.
Angew. Chem. Int. Ed.
2008,
47:
6960
8d See also ref. 5a
8e
Lee S.-g.
Chem. Commun.
(Cambridge)
2006,
1049
9a
Bergbreiter DE.
Tian J.
Hongfa C.
Chem. Rev.
2009,
109:
530
9b
Wang Z.
Chen G.
Ding K.
Chem.
Rev.
2009,
109:
322
9c
Lu J.
Toy PH.
Chem. Rev.
2009,
109:
815
9d
Ikegami S.
Hamamoto H.
Chem. Rev.
2009,
109:
583
9e
Bergbreiter DE.
Sung SD.
Adv.
Synth. Catal.
2006,
348:
1352
10
Zhang W.
Chem.
Rev.
2009,
109:
749
11
Lombardo M.
Trombini C.
ChemCatChem
2010,
2:
135
12a
Baker RT.
Tumas W.
Science
(Washington, DC, U.S.)
1999,
284:
1477
12b
Gladysz JA.
Science (Washington, DC, U.S.)
1994,
266:
55
12c
Horváth IT.
Rábai J.
Science (Washington,
DC, U.S.)
1994,
266:
72
13
Kodera Y.
Matsushima A.
Hiroto M.
Nishimura H.
Ishii A.
Ueno T.
Inada Y.
Prog.
Polym. Sci.
1998,
23:
1233
14a
Bergbreiter DE.
Chem. Rev.
2002,
102:
3345
14b
Dickerson TJ.
Reed NN.
Janda KD.
Chem. Rev.
2002,
102:
3325
15
Behr A.
Henze G.
Schomäcker R.
Adv.
Synth. Catal.
2006,
348:
1485
16
Lu N.
Chen Y.-C.
Chen W.-S.
Chen TL.
Wub S.-J.
J.
Organomet. Chem.
2009,
694:
278
17
Yoshida A.
Hao X.
Nishikido J.
Green
Chem.
2003,
5:
554
18
Hao X.
Yoshida A.
Nishikido J.
Green
Chem.
2004,
6:
566
19
Hao X.
Yoshida A.
Nobuto H.
J. Fluorine
Chem.
2007,
128:
1396
20
Feng C.
Wang Y.
Jiang J.
Yang Y.
Yu F.
Jin Z.
J.
Mol. Catal. A: Chem.
2006,
248:
159
21
Lombardo M.
Chiarucci M.
Trombini C.
Green
Chem.
2009,
11:
574
22a
Alimardanov A.
Schmieder-van de Vondervoort L.
de Vries AHM.
de Vries JG.
Adv. Synth. Catal.
2004,
346:
1812
22b
Beletskaya IP.
Cheprakov AV.
Chem.
Rev.
2000,
100:
3009
23
Azoui H.
Baczko K.
Cassel S.
Larpent C.
Green Chem.
2008,
10:
1197
24
Zarka MT.
Bortenschlager M.
Wurst K.
Nuyken O.
Weberskirch R.
Organometallics
2004,
23:
4817
25
Mąkosza M.
Fedoryński M.
Catal. Rev.
2003,
45:
321
26
Cassani C.
Bernardi L.
Fini F.
Ricci A.
Angew. Chem. Int. Ed.
2009,
48:
5694
27
Hashimoto T.
Maruoka K.
Chem. Rev.
2007,
107:
5656
28
Mąkosza M.
Serafinowa B.
Rocz. Chem.
1965,
39:
1223
29a
Adams CJ.
Earle MJ.
Seddon KR.
Green Chem.
2000,
2:
21
29b
Roberts G.
Chem.
Commun. (Cambridge)
1998,
2097
30a
Pucheault M.
Vaultier M.
Top.
Curr. Chem.
2010,
290:
83
30b
Fei ZF.
Geldbach TJ.
Zhao DB.
Dyson PJ.
Chem.
Eur. J.
2006,
12:
2123
31
Davis JH.
Wierzbicki A.
Proceedings of the Symposium on Advances in
Solvent Selection and Substitution for Extraction
American
Institute of Chemical Engineers;
New York:
2000.
32a
Riisager A.
Fehrmann R.
Haumann M.
Wasserscheid P.
Eur.
J. Inorg. Chem.
2006,
695
32b
Riisager A.
Fehrmann R.
Flicker S.
van Hal R.
Haumann M.
Wasserscheid P.
Angew. Chem. Int. Ed.
2005,
44:
185
33
Mehnert CP.
Chem.
Eur. J.
2004,
11:
50
34a
Lombardo M.
Trombini C. In
Eco-Friendly Synthesis of Fine Chemicals
Ballini R.
Royal Society of Chemistry;
Cambridge:
2009.
p.1-79
34b
Trombini C.
Lombardo M. In Green
Chemical Reactions
Tundo P.
Esposito V.
Springer;
Dordrecht:
2008.
p.37-78
35
Ruta M.
Laurenczy G.
Dyson PJ.
Kiwi-Minsker L.
J. Phys. Chem.
C
2008,
112:
17814
36
Tundo P.
Perosa A.
Chem. Soc. Rev.
2007,
36:
532
37
Perosa A.
Tundo P.
Selva M.
Zinovyev S.
Testa A.
Org. Biomol.
Chem.
2004,
2:
2249
38a
Migowski P.
Dupont J.
Chem.
Eur. J.
2007,
13:
32
38b
Roucoux A.
Schulz J.
Patin H.
Chem.
Rev.
2002,
102:
3757
39
Paganelli S.
Perosa A.
Selva M.
Adv.
Synth. Catal.
2007,
349:
1858
40
Yang X.
Fei Z.
Zhao D.
Ang WH.
Li Y.
Dyson PJ.
Inorg. Chem.
2008,
47:
3292
41
Chauvin Y.
Olivier-Bourbigou H.
Chem. Tech.
1995,
26
42
ŒledŸ P.
Mauduit M.
Grela K.
Chem. Soc. Rev.
2008,
37:
2433
43
Clavier H.
Audic N.
Mauduit M.
Guillemin J.-C.
Chem. Commun. (Cambridge)
2004,
2282
44
Garber SB.
Kingsbury JS.
Gray BL.
Hoveyda AH.
J.
Am. Chem. Soc.
2000,
122:
8168
45
Roy M.-N.
Poupon J.-C.
Charette AB.
J.
Org. Chem.
2009,
74:
8510
46a
Gao J.
Ma S.
Major DT.
Nam K.
Pu J.
Truhlar
DG.
Chem.
Rev.
2006,
106:
3188
46b
Warshel A.
Sharma PK.
Kato M.
Xiang Y.
Liu H.
Olsson MHM.
Chem. Rev.
2006,
106:
3210
47
Bini R.
Chiappe C.
Llopsis Mestre V.
Pomelli CS.
Welton T.
Org.
Biomol. Chem.
2008,
6:
2522
48
Rideout DC.
Breslow R.
J. Am. Chem. Soc.
1980,
102:
7816
49
Pirrung MC.
Chem.
Eur. J.
2006,
12:
1312
50
Dwars T.
Paetzold E.
Oehme G.
Angew.
Chem. Int. Ed.
2005,
44:
7174
51
Vriezema DM.
Aragonès MC.
Elemans JAAW.
Cornelissen JJLM.
Rowan AE.
Nolte RJM.
Chem. Rev.
2005,
105:
1445
52
Fuji K.
Morimoto T.
Tsutsumi K.
Kakiuchi K.
Angew. Chem. Int. Ed.
2003,
42:
2409
53
Lipshutz BH.
Aguinaldo GT.
Ghorai S.
Voigtritter K.
Org. Lett.
2008,
10:
1325
54 Borowy-Borowski H, Sikorska-Walker M, and Walker PR. inventors; US Patent 6632443.
55
Narayan S.
Muldoon J.
Finn MG.
Fokin VV.
Kolb HC.
Sharpless KB.
Angew. Chem. Int.
Ed.
2005,
44:
3275
56
Gruttadauria M.
Giacalone F.
Noto R.
Adv.
Synth. Catal.
2009,
351:
33
57
Klijn JE.
Engberts JBFN.
Nature
(London)
2005,
435:
746
58
Jung Y.
Marcus RA.
J. Am. Chem. Soc.
2007,
129:
5492
59a
List B.
Lerner RA.
Barbas CF.
J. Am.
Chem. Soc.
2000,
122:
2395
For a comprehensive review on enamine-based organocatalysis,
see:
59b
Mukherjee S.
Yang JW.
Hoffmann S.
List B.
Chem. Rev.
2007,
107:
5471
60a
Kotrusz P.
Kmentová I.
Gotov B.
Toma Š.
Solčániová E.
Chem.
Commun. (Cambridge)
2002,
2510
60b
Loh T.-P.
Feng L.-C.
Yang H.-Y.
Yiang J.-Y.
Tetrahedron Lett.
2002,
43:
8741
61
Lombardo M.
Pasi F.
Easwar S.
Trombini C.
Adv. Synth. Catal.
2007,
349:
2061
62
Hayashi Y.
Sumiya T.
Takahashi J.
Gotoh H.
Urushima T.
Shoji M.
Angew. Chem. Int. Ed.
2006,
45:
972
63
Huang J.
Zhang X.
Armstrong DW.
Angew.
Chem. Int. Ed.
2007,
46:
9073
64
Mase N.
Nakai Y.
Ohara N.
Yoda H.
Takabe K.
Tanaka F.
Barbas CF.
J.
Am. Chem. Soc.
2006,
128:
734
65
Lin J.-H.
Zhang C.-P.
Xiao J.-C.
Green
Chem.
2009,
11:
1750
66a
Isart C.
Bures J.
Vilarrasa J.
Tetrahedron Lett.
2008,
49:
5414
66b
Zotova N.
Franzke A.
Armstrong A.
Blackmond DG.
J. Am. Chem. Soc.
2007,
129:
15100
66c
Seebach D.
Beck AK.
Badine DM.
Limbach M.
Eschenmoser A.
Treasurywala AM.
Hobi R.
Prikoszovich W.
Linder B.
Helv.
Chim. Acta
2007,
90:
425
66d
List B.
Hoang L.
Martin HJ.
Prod.
Natl. Acad. Sci. U.S.A.
2004,
101:
5839
67
Lombardo M.
Pasi F.
Easwar S.
Trombini C.
Synlett
2008,
2471
68
Lombardo M.
Easwar S.
De Marco A.
Pasi F.
Trombini C.
Org.
Biomol. Chem.
2008,
6:
4224
69
Phan L.
Chiu D.
Heldebrant DJ.
Huttenhower H.
John E.
Li X.
Pollet P.
Wang R.
Eckert CA.
Liotta CL.
Jessop PG.
Ind.
Eng. Chem. Res.
2008,
47:
539
70
Phan L.
Jessop PG.
Green Chem.
2009,
11:
307
71
Desset SL.
Cole-Hamilton DJ.
Angew. Chem.
Int. Ed.
2009,
48:
1472
72
Geldbach TJ.
Dyson PJ.
J. Am. Chem. Soc.
2004,
126:
8114
73
Ding X.
Tang W.
Zhu C.
Cheng Y.
Adv. Synth. Catal.
2010, Early
View
74
Lombardo M.
Easwar S.
Pasi F.
Trombini C.
Dhavale DD.
Tetrahedron
2008,
64:
9203
75a
Zhu S.
Yu S.
Ma D.
Angew. Chem. Int. Ed.
2008,
47:
545
75b
Hayashi Y.
Okano T.
Aratake S.
Hazelard D.
Angew. Chem. Int. Ed.
2007,
46:
4922
75c
Hayashi Y.
Gotoh H.
Hayasi T.
Shoji M.
Angew. Chem. Int. Ed.
2005,
44:
4212
76
Lombardo M.
Chiarucci M.
Quintavalla A.
Trombini C.
Adv. Synth. Catal.
2009,
351:
2801
77
Cozzi PG.
Benfatti F.
Zoli L.
Angew.
Chem. Int. Ed.
2009,
48:
1313
78 Quintavalla, A. unpublished results.
79
Kizirian JC.
Chem.
Rev.
2008,
108:
140
80
Yao Q.
Angew.
Chem. Int. Ed.
2000,
39:
3896
81
Walsh PJ.
Li H.
de Parrodi CA.
Chem.
Rev.
2007,
107:
2503
82
Lombardo M.
Easwar S.
De Marco A.
Pasi F.
Trombini C.
Adv.
Synth. Catal.
2009,
351:
276
83
Hayashi Y.
Aratake S.
Itoh T.
Okano T.
Sumiya T.
Shoji M.
Chem.
Commun. (Cambridge)
2007,
957
84
Almaºi D.
Alonso DA.
Balaguer AN.
Nájera C.
Adv. Synth.
Catal.
2009,
351:
1123
85
Mason BP.
Price KE.
Steinbacher JL.
Bogdan AR.
McQuade DT.
Chem. Rev.
2007,
107:
2300
86a
Wiles C.
Watts P.
Eur.
J. Org. Chem.
2008,
1655
86b See also ref. 7b
87
Zayed F.
Greiner L.
Schulz PS.
Lapkin A.
Leitner W.
Chem.
Commun. (Cambridge)
2008,
79
88a
Ruta M.
Yuranov I.
Dyson PJ.
Laurenczy G.
Kiwi-Minsker L.
J. Catal.
2007,
247:
269
88b
Riisager A.
Jorgensen B.
Wasserscheid P.
Fehrmann R.
Chem. Commun. (Cambridge)
2006,
994
88c
Riisager A.
Fehrmann R.
Haumann M.
Wasserscheid P.
Eur. J. Inorg. Chem.
2006,
695
88d See also ref. 33
89
Hintermair U.
Zhao G.
Santini CC.
Muldoon MJ.
Cole-Hamilton DJ.
Chem. Commun. (Cambridge)
2007,
1462
90
Riisager A.
Wasserscheid P.
van Hal R.
Fehrmann R.
J. Catal.
2003,
219:
452
91
Hintermair U.
Höfener T.
Pullmann T.
Franciò G.
Leitner W.
ChemCatChem
2010,
2:
150
92
Kashid MN.
Kiwi-Minsker L.
Ind. Eng. Chem. Res.
2009,
48:
6465
93
Doku GN.
Verboom W.
Reinhoudt DN.
van den Berg A.
Tetrahedron
2005,
61:
2733
94
Fukuyama T.
Rahman MdT.
Sato M.
Ryu I.
Synlett
2008,
151
95
Pohar A.
Plazl I.
nidaršič-Plazl P.
Lab Chip
2009,
9:
3385