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ONE-POT SYNTHESES USING CARBONYL COMPOUNDS CATALYZED BY CE(III) SUPPORTED ON A WEAKLY ACIDIC CATION-EXCHANGER RESIN Eva Havrnkov , Pavel Pazdera* *E-mail: pazdera@chemi.muni.cz, havrankovae@gmail.com Centre for Syntheses at Sustainable

  1. ONE-POT SYNTHESES USING CARBONYL COMPOUNDS CATALYZED BY CE(III) SUPPORTED ON A WEAKLY ACIDIC CATION-EXCHANGER RESIN Eva Havránková , Pavel Pazdera* *E-mail: pazdera@chemi.muni.cz, havrankovae@gmail.com Centre for Syntheses at Sustainable Conditions and Their Management, Department of Chemistry, Faculty of Science, Masaryk University, UKB, Kamenice 753/5, CZ-625 00 Brno, Czech Republic.

  2. Introduction One of the possibilities to sophisticate compound syntheses is catalysis using supported catalyst which combines the advantages of both homogeneous and heterogeneous catalyst. An application of Ce(III) inorganic salts, first of all CeCl 3 .7H 2 O doped by sodium iodide, not until has been described from start of 21st Century. Twenty communications has been present during this time only. Catalysis by Ce(III) salts has been used for an activation of carbonyl compounds and their derivatives in syntheses. Easily available, cheap and mechanically and thermally stable industrial cation-exchangers may be used as carriers 1 . These in connection with complex of cerium in oxidation state of 3 + provide an effective, easily separable and recyclable catalytic system. This system has been studied with a view to its possible synthetic applications on model three-component domino syntheses, i.e. Kabachnik-Fields one-pot synthesis of α - aminophosphonates 2 , and Prins-Ritter one-pot synthesis of 4-amidotetrahydropyran derivatives 3 , respectively.

  3. Preparation of catalysts 1) Preparation of 30 mol% CeCl 3 .7H 2 O and 30 mol% of NaI supported on silica gel 4 : Silica gel was added to a mixture of CeCl 3 .7H 2 O and NaI in acetonitrile, and the mixture was stirred overnight at room temperature. The acetonitrile was removed by rotary evaporator and the resulting mixture was used as a catalyst. 2) Preparation of cation Ce(III) supported on a weak acid macroporous cation-exchanger resin (D113 Noromite; 4.5 mol/l) 1 : Resin and water were stirred for 5 min. Than was slowly added a solution of sodium carbonate to pH cca 12. Subsequently, the aqueous phase was decanted and the solid phase was washed with of water. The solid phase was stirred with a solution of CeCl 3 .7H 2 O in water overnight. The aqueous phase was again decanted and the solid phase washed with water and methanol, respectively. Finally, the thus prepared catalyst was dried under vacuum at room temperature to constant weight. The Ce(III) capacity in this resin was 2.3 mmol/g. An equivalent amount of NaI or eventual proline such as supported Ce(III) catalyst was added into a reaction mixture.

  4. Preparation of α -aminophosphonates • Scheme of the reaction: O OEt P H OEt OEt O O P NH catalytic system OEt H Ar NH 2 + + Ar ethanol, r .t. H O R H R P OEt EtO • Key cerium containing intermediate for Kabachnik-Fields synthesis: H R 3+ Ce N H R O R 3+ Ce N EtO H 3+ P O R Ce R EtO H

  5. Preparation of α -aminophosphonates – table of results Reactants Catalyst Molar Yield Time Ratio [eqv] [%] [min] Benzaldehyde; - 1 : 1,1 N.R. 1440 Aniline; CeCl 3 .7H 2 O 2 1 : 1,1 : 0,03 95 300 Diethyl phosphite CeCl 3 .7H 2 O/NaI 1 : 1,1 : 0,03 96 240 CeCl 3 .7H 2 O/NaI supported on resin 1 : 1,1 : 0,03 98 220 CeCl 3 .7H 2 O/NaI supported on silica gel 1 : 1,1 : 0,03 93 330 Proline/CeCl 3 .7H 2 O/NaI supported on resin 1 : 1,1 : 0,03 96 180 4-CH 3 O- - 1 : 1,1 N.R. 1440 Benzaldehyde; CeCl 3 .7H 2 O 2 1 : 1,1 : 0,03 91 270 Aniline; Diethyl CeCl 3 .7H 2 O/NaI 1 : 1,1 : 0,03 93 240 phosphite CeCl 3 .7H 2 O/NaI supported on resin 1 : 1,1 : 0,03 93 180 CeCl 3 .7H 2 O/NaI supported on silica gel 1 : 1,1 : 0,03 90 280 Proline/CeCl 3 .7H 2 O/NaI supported on resin 1 : 1,1 : 0,03 94 150 *At room temperature; ethanol as a solvent.

  6. Preparation of α -aminophosphonates – table of results Reactants Catalyst Molar Yield Time Ratio [eqv] [%] [min] 4-NO 2 - - 1 : 1,1 N.R. 1440 Benzaldehyde; CeCl 3 .7H 2 O 2 1 : 1,1 : 0,03 90 780 Aniline; Diethyl CeCl 3 .7H 2 O/NaI 1 : 1,1 : 0,03 92 660 phosphite CeCl 3 .7H 2 O/NaI supported on resin 1 : 1,1 : 0,03 94 600 CeCl 3 .7H 2 O/NaI supported on silica gel 1 : 1,1 : 0,03 90 780 Proline/CeCl 3 .7H 2 O/NaI supported on resin 1 : 1,1 : 0,03 94 420 Benzaldehyde; - 1 : 1,1 N.R. 1440 4-Cl-Aniline; CeCl 3 .7H 2 O 2 1 : 1,1 : 0,03 93 540 Diethyl phosphite CeCl 3 .7H 2 O/NaI 1 : 1,1 : 0,03 94 420 CeCl 3 .7H 2 O/NaI supported on resin 1 : 1,1 : 0,03 97 360 CeCl 3 .7H 2 O/NaI supported on silica gel 1 : 1,1 : 0,03 91 560 Proline/CeCl 3 .7H 2 O/NaI supported on resin 1 : 1,1 : 0,03 96 270 *At room temperature; ethanol as a solvent.

  7. Preparation of α -aminophosphonates – table of results Reactants Catalyst Molar Yield Time Ratio [eqv] [%] [min] Benzaldehyde; - 1 : 1,1 N.R. 1440 4-Aminophenol; CeCl 3 .7H 2 O 2 1 : 1,1 : 0,03 90 600 Diethyl phosphite CeCl 3 .7H 2 O/NaI 1 : 1,1 : 0,03 94 420 CeCl 3 .7H 2 O/NaI supported on resin 1 : 1,1 : 0,03 96 350 CeCl 3 .7H 2 O/NaI supported on silica gel 1 : 1,1 : 0,03 93 510 Proline/CeCl 3 .7H 2 O/NaI supported on resin 1 : 1,1 : 0,03 96 280 *At room temperature; ethanol as a solvent.

  8. Preparation of 4-amidotetrahydropyranes • Scheme of the reaction: NHCOMe O OH H + catalytic system/AcCl + CH 3 CN O CH 3 CN, r .t. R R • Key cerium containing intermediate for Prins-Ritter synthesis: 3+ Ce R O O R H + 3+ O Ce R H

  9. Preparation of 4-amidotetrahydropyranes – table of results Reactants Catalyst Molar Ratio Yield Time [eqv] [%] [min] Acetyl chloride; - 1,5 : 1,2 : 1 31 1440 But-3-en-1-ol; CeCl 3 .7H 2 O/NaI 3 1,5 : 1,2 : 1 : 0,05 84 420 Benzaldehyde CeCl 3 .7H 2 O/NaI supported on resin 1,5 : 1,2 : 1 : 0,05 86 360 CeCl 3 .7H 2 O/NaI supported on silica gel 1,5 : 1,2 : 1 : 0,05 82 450 Acetyl chloride; - 1,5 : 1,2 : 1 45 1440 But-3-en-1-ol; CeCl 3 .7H 2 O/NaI 3 1,5 : 1,2 : 1 : 0,05 93 360 4-CH 3 O- Benzaldehyde CeCl 3 .7H 2 O/NaI supported on resin 1,5 : 1,2 : 1 : 0,05 93 220 CeCl 3 .7H 2 O/NaI supported on silica gel 1,5 : 1,2 : 1 : 0,05 89 360 *At room temperature; acetonitrile as a solvent.

  10. Preparation of 4-amidotetrahydropyranes – table of results Reactants Catalyst Molar Ratio Yield Time [eqv] [%] [min] Acetyl chloride; - 1,5 : 1,2 : 1 38 1440 But-3-en-1-ol; CeCl 3 .7H 2 O/NaI 3 1,5 : 1,2 : 1 : 0,05 82 450 4-NO 2 - Benzaldehyde CeCl 3 .7H 2 O/NaI supported on resin 1,5 : 1,2 : 1 : 0,05 84 340 CeCl 3 .7H 2 O/NaI supported on silica gel 1,5 : 1,2 : 1 : 0,05 80 480 Acetyl chloride; - 1,5 : 1,2 : 1 35 1440 But-3-en-1-ol; CeCl 3 .7H 2 O/NaI 3 1,5 : 1,2 : 1 : 0,05 90 480 Cyclohexanone CeCl 3 .7H 2 O/NaI supported on resin 1,5 : 1,2 : 1 : 0,05 91 400 CeCl 3 .7H 2 O/NaI supported on silica gel 1,5 : 1,2 : 1 : 0,05 88 500 *At room temperature; acetonitrile as a solvent.

  11. Conclusion It was discovered that cation Ce(III) supported on a weak acid macroporous cation-exchanger shown in the studied reactions at least the same or better catalytic activity as salt CeCl 3 .7H 2 O, eventually doped by NaI. In conclusion, we developed a novel and environmentally friendly catalyst, which can be used in a wide range of reactions of carbonyl and other compounds. The catalyst can be used repeatedly. The used organic resin has not abrasive effect on surface of reaction vessels, in contradistinction to silica gel carrier. The advantages of the present protocol are mild, heterogeneous conditions, shorter reaction times, easy work-up, and low toxicity, inexpensive, ready availability, recoverability, recyclability of the catalyst that make the procedure an attractive alternative to the existing methods for the synthesis of α -aminophosphonates, and 4- amidotetrahydropyran derivatives.

  12. References 1. Pazdera, P.; Zberovská, B.; Němečková , D.; Datinská, V. : CZ 2011/0799 (A3). 2. Jafari, A. A.; Nazarpour, M., Abdollahi-Alibeik, M.; Heteroatom Chemistry, 2010 , 21, 397-403. 3. Yadav, J. S.; Subba Reddy, B. V.; Narayana Kumar, G. G. K. S.; Madhusudhan Reddy, G.; Tetrahedron Letters, 2007 , 48, 4903-4906. 4. Bartoli, G.; Bartolacci, M.; Bosco, M.; et al. : J. Org. Chem., 2003 , 68 (11), 4595-4597.

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