Recent Advances in IMCRs (Passerini and Ugi Reac5ons) Anil Kumar Gupta Group Mee5ng May 16,2008
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1 Recent Advances in IMCRs (Passerini and Ugi Reac5ons) Anil Kumar Gupta Group Mee5ng May 16,2008
2 Mul5component Reac5ons 100 % yield Simple Total Conversion One pot safe Resource effec5ve Environmental Friendly Readily Available Star5ng Materials Multicomponent Reactions (MCRs) are general defined as reactions where more than two starting materials to react to form a product, incorporating essentially all of the atoms of the educts. Generally, there are different classification schemes of MCRs possible, e.g. according to the reaction mechanisms, the components involved, or the intrinsic variability.
3 Diversity in Mul5component Reac5ons The union of two highly variable MCRs, the Petasis and Ugi reaction: Since both reactions use starting material which are commercially available in very large quantities. Theoretically, this combination of MCRs spans a chemical space of greater than =10 14 small molecules. This constitutes a combination of MCRs of very high variability. An interesting fact about isocyanides: The more long-term inhalation of isocyanides is said to increase the intensity of dreams at night. Portlock, D. E.; Naskar, D.; West, L.; Ostaszewski, R.; Chen, J. J.Tetrahedron Le,. 2003, 44, 5121.
4 The Passerini Reac5on (developed in 1921) Mario Passerini ( ), the inventor of one of the most significant isocyanide based MCRs. Mechanism of Passerini Reaction α acyloxycarboxamide R 3 Accelerated in apro5c solvents needed: THF, DCM, MeCN etc.
5 Diastereoselec5ve Passerini Reac5on Chiral Isocyanides Chiral Aldehydes H. Bock, I. Ugi, J. Prakt. Chem. 1997, 339, 385. Chiral Acids L. Banfi, G. Guan5, R. Riva, Chem. Comm. 2000, 985. R. Frey, S. G. Galbraith, S. Guelfi, C. Lamberth, M. Zeller, Synle, 2003, 1536.
6 Denmark, S.E.; Fan, Y. J. Am. Chem. Soc. 2003, 125, 7825 Denmark, S.E.; Fan, Y. J. Org. Chem. 2005, 70, 9667 Enan5oselec5ve Passerini Type Reac5on
7 Enan5oselec5ve Passerini Reac5on (1) THF, rt, 12 h Catalyst loading: 100 mol% or 50 mol% Ti(O i Pr) 4 : Ligand = 1:1 U. Kusebauch, B. Beck, K. Messer, E. Herdtweck, A. Domling Org. Le,. 2003, 5, 4021.
8 Enan5oselec5ve Passerini Reac5on (1) Solvents Ether THF DCM Toluene Dioxane U. Kusebauch, B. Beck, K. Messer, E. Herdtweck, A. Domling Org. Le,. 2003, 5, 4021.
9 Enan5oselec5ve Passerini Reac5on (1) U. Kusebauch, B. Beck, K. Messer, E. Herdtweck, A. Domling Org. Le,. 2003, 5, 4021.
10 Enan5oselec5ve Passerini Reac5on (2) 4 = indan pybox Cu II complex Andreana, P.R.; Liu, C.C.; Schreiber, S.L. Org. Le,. 2004, 6, 4231.
11 Enan5oselec5ve Passerini Reac5on (2) bidentate (S,S) bis(oxazolinyl) (box) (1 & 2) Cu(II) Anhydrous condi5ons were necessary to avoid background reac5on by water) tridentate bis(oxazolinyl)pyridine (pybox) (3 & 4) Cu(II) Andreana, P.R.; Liu, C.C.; Schreiber, S.L. Org. Le,. 2004, 6, 4231.
12 Enan5oselec5ve Passerini Reac5on (2) Limita5on: Chela5ng aldehydes needed, no diversity in acid component Andreana, P.R.; Liu, C.C.; Schreiber, S.L. Org. Le,. 2004, 6, 4231.
13 Enan5oselec5ve Passerini Reac5on (3) 16 examples Wang, S. X.; Wang, M. X.; Wang, D. X.; Zhu, J. Angew. Chem. Int. Ed. 2008, 47, 388
14 Enan5oselec5ve Passerini Reac5on (3) Several pijalls exist that make this task par5cularly challenging: 1) The complexity of the reac5on mechanism Possible Solu5on: To use a chiral catalyst with a single coordina5on site & Slow addi5on of the acid component to avoid the background reac5on 2) The compe55veness of the uncatalyzed background reac5on 3) The poten5al of the three components, all of which are Lewis bases, to coordinate to or deac5vate the catalyst 4) The problem of catalyst turnover as a result of product inhibi5on. The P 3CR adduct itself is also a bidentate ligand and can therefore compete with the substrate to coordinate to the catalyst 5) When a nonchela5ng aldehyde is used, the reac5on produces an imidate intermediate A that is bidentate in nature. Wang, S. X.; Wang, M. X.; Wang, D. X.; Zhu, J. Angew. Chem. Int. Ed. 2008, 47, 388
15 Enan5oselec5ve Passerini Reac5on (3) Op5mized Condi5ons Concentra5on = 0.33M Solvent = toluene Tempearture = 40 C Time = 48 h Slow addi5on of acid Wang, S. X.; Wang, M. X.; Wang, D. X.; Zhu, J. Angew. Chem. Int. Ed. 2008, 47, 388
16 Enan5oselec5ve Passerini Reac5on (3) (53%)* * t BuNC used OMe Varia5ons Acid and Isocyanide ( Aroma5c aldehydes Failed) OMe OMe Wang, S. X.; Wang, M. X.; Wang, D. X.; Zhu, J. Angew. Chem. Int. Ed. 2008, 47, 388
17 Enan5oselec5ve Passerini Reac5on (3) (53%)* OMe OMe OMe OMe OMe OMe OMe Wang, S. X.; Wang, M. X.; Wang, D. X.; Zhu, J. Angew. Chem. Int. Ed. 2008, 47, 388
18 The Ugi Reac5on Ivar Karl Ugi ( ), the inventor of the most diversified IMCRs. α N acylamino amide Ugi, I. Angew. Chem. Int. Ed. 1962, 1, 8.
19 The Ugi Reac5on
20 Four Component Approach Ugi Reac5on
21 General Requirements for Ugi Reac5on Highly nucleophilc amine recommended Electron rich aldehydes favor the reac5on. Preformed Imines from ketones also react ( Yamada, 1998, synthesis, 991) Strong Acids Usually at room temperatures. Low temp some5mes(ugi, 1991,Synthesis, 1095) High Concentra5on of the reactants Pre forma5on of imines gives good yields. Polar solvents like Methanol. Toluene ( with high temp), ether and CH 2 Cl 2 are also used. High Pressure
22 Cristau, P., Vors, J.P. & Zhu, J. Org. Le,. 2001, 3, Ugi Reac5on in Toluene
23 Alternate Mechanism: Diastereoselec5ve Ugi Reac5on: Chiral Isocyanides Banfi, L., Basso, A., Guan5, G. & Riva, R. Asymmetric isocyanide based MCRs. In Mul5component Reac5ons (eds. Zhu, J. & Bienayme, H.) 1 32 (Wiley VCH, Weinheim, Germany, 2005).
24 Diastereoselec5ve Ugi Reac5on: Chiral Amines Ugi, K. Offermann Angew. Chem. Int. Ed. Engl. 1963, 2, 624. D. Marquarding, P. Hoffmann, H. Heitzer, I. Ugi, J. Am. Chem. Soc. 1970, 92, 1969.
25 Diastereoselec5ve Ugi Reac5on: Chiral Aldehydes No racemiza5on if OBn or OTBDMS at C 2 posi5on of aldehyde Kelly, C. L.; Lawrie, K. W. M.; Morgan, P.; Willis, C. L. Tetrahedron Le,. 2000, 41, 8001.
26 Three Component Approach Ugi Reac5on
27 Acid Free Three Component Ugi Reac5on U5lizing Secondary Amines Tanaka, Y.; Hasui, T.; Suginome, M. Org. Le,. 2007, 9, 4407
28 Acid Free Three Component Ugi Reac5on U5lizing Secondary Amines Tanaka, Y.; Hasui, T.; Suginome, M. Org. Le,. 2007, 9, 4407
29 Acid Free Three Component Ugi Reac5on U5lizing Secondary Amines Tanaka, Y.; Hasui, T.; Suginome, M. Org. Le,. 2007, 9, 4407
30 Acid Free Three Component Ugi Reac5on U5lizing Secondary Amines Major Difference from normal Ugi Reac5on: Non acidic nature of the reac5on system Tanaka, Y.; Hasui, T.; Suginome, M. Org. Le,. 2007, 9, 4407
31 List, B.; Pan, S. C. Angew. Chem. Int. Ed, 2008, 47, 3622 Cataly5c Three Component Ugi Reac5on
32 List, B.; Pan, S. C. Angew. Chem. Int. Ed, 2008, 47, 3622 Cataly5c Three Component Ugi Reac5on
33 Cataly5c Three Component Ugi Reac5on : Solvent Study List, B.; Pan, S. C. Angew. Chem. Int. Ed, 2008, 47, 3622
34 Cataly5c Three Component Ugi Reac5on : Temperature Study List, B.; Pan, S. C. Angew. Chem. Int. Ed, 2008, 47, 3622
35 Cataly5c Three Component Ugi Reac5on: Substrate Scope List, B.; Pan, S. C. Angew. Chem. Int. Ed, 2008, 47, 3622
36 Cataly5c Three Component Ugi Reac5on: Substrate Scope List, B.; Pan, S. C. Angew. Chem. Int. Ed, 2008, 47, 3622
37 Cataly5c Three Component Ugi Reac5on: Substrate Scope Catalyst TRIP Chiral phosphinic acid Yield 15 % 90% ee 18 % 04 % List, B.; Pan, S. C. Angew. Chem. Int. Ed, 2008, 47, 3622
38 Synthesis of Aziridines via Ugi Reac5on Banfi, L.; Basso, A.; Guan5, G.; Paravidino, M.; Riva, R QSAR Comb.Sci. 25, 2006, 457
39 Synthesis of Aziridines via Ugi Reac5on Banfi, L.; Basso, A.; Guan5, G.; Paravidino, M.; Riva, R QSAR Comb.Sci. 25, 2006, 457
40 Diastereoselec5ve Ugi Reac5on (3CR): Chiral Imines Ugi, K. Offeremann, H. Herlinger, D. Marquarding, Justus Liebigs Ann. Chem. 1967, 1. S. Lehnhoff, M. Goebel, R. M. Karl, R. Klsel, I. Ugi, Angew. Chem. Int. Ed. 1995, 34, 1104.
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