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Selected Catalytic Reactions Involving Selenium Compounds. Carl Trudel, Literature Meeting Wednesday, April 11 th 2012. About this presentation. Singh, F. V.; Wirth, T. In Organoselenium Chemistry ; Wiley-VCH Verlag GmbH & Co. KGaA, 2012, p 321-360.
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Selected Catalytic Reactions Involving Selenium Compounds Carl Trudel, Literature Meeting Wednesday, April 11th 2012
About this presentation • Singh, F. V.; Wirth, T. In Organoselenium Chemistry; Wiley-VCH Verlag GmbH & Co. KGaA, 2012, p 321-360. • Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Selenium and Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p 251-283.
Presentation Schedule • Some selenium facts • Stoichiometric reactions • Selenium as a catalyst • Carbonylation • Oxidation (B.-V., epoxidation, selenylation-deselenylation, alkyne, allylic, alcohol, imine, aniline...) • Halobromation • GPx like activity • Alkylation • Selenium as a ligand for • Copper • Palladium
Fun Facts • Discovered by J. J. Berzelius in 1817. • Selenium => Selene (moon) • Chalcogen (O, S, Te) • Among the 25 least common elements • 0.05 – 0.09 ppm in the earth crust • Recommended daily intake: 55µg (max 400µg/day) • >1000µg/day => intoxications • Brazil nuts, fishes and seafood (oyster and tuna)... • North American cereals (Beer!) Berzelius, J. J. Afhandl. Fys. KemiMineralogi.1818, 42. Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Selenium and Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p 285-302. http://www.passeportsante.net/fr/Solutions/PlantesSupplements/Fiche.aspx?doc=selenium_ps [April 2012]
Other Facts and Nomenclature • Used in everyday applications • Glass-making, electronics, printers, solar cells • Glutathione peroxidase enzymes and selenoproteines • Antioxidants, antitumor, antimicrobial, antiviral • Se(s) 44.84 $/mol • SeO2 54.59 $/mol • Ph2Se 4 768.33 $/mol • (PhSe)2 3 970,29 $/mol • [mCPBA 120.11 $/mol] www. sigmaaldrich.com [april 2012]
Soichiometric Selenium Chemistry Thompson, D. P.; Boudjouk, P. J. Org. Chem.1988, 53, 2109-2112. Reich, H. J.; Cohen, M. L.; Clark, P. S. Org. Synth. 1988, 50-9, 533-537. Santi, C.; Wirth, T. Tetrahedron: Asymm.1999, 10, 1019-1023.
1st Selenium Catalyzed Reaction • Carbonylation of aminoalcohols Sonoda, N.; Yamamoto, G.; Natsukawa, K.; Kondo, K.; Murai, S. Tetrahedron Lett. 1975, 16, 1969-1972.
Selenium Based Oxygen Transfer Reagents • Perseleninic acid • Hydroxy Perhydroxy Selenane Davis, F. A.; Reddy, R. T. J. Org. Chem. 1992, 57, 2599-2606.
Baeyer-Villiger Reaction Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Seleniumand Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p 251-283.
Baeyer-Villiger Reaction, Perseleninic Acids Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Seleniumand Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p 251-283.
Catalytic Baeyer-Villiger Reaction Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Seleniumand Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p 251-283.
Catalytic Baeyer-Villiger Reaction ten Brink, G.-J.; Vis, J.-M.; Arends, I. W. C. E.; Sheldon, R. A. J. Org. Chem. 2001, 66, 2429.
Catalytic Baeyer-Villiger Reaction • C3° > C2° > Bn > Ar/H* > C1° > Me • CF3CH2OH, 20 °C • Hydrolysis might be an issue • Important substituent effect ten Brink, G.-J.; Vis, J.-M.; Arends, I. W. C. E.; Sheldon, R. A. J. Org. Chem. 2001, 66, 2429.
Seleninic Acid Epoxidation • Pioneer work by Sharpless Hori, T.; Sharpless, K. B. J. Org. Chem. 1978, 43, 1689-1697.
Seleninic Acid Epoxidation • Pioneer work by Sharpless Hori, T.; Sharpless, K. B. J. Org. Chem. 1978, 43, 1689-1697.
Seleninic Acid Epoxidation • DCM or trifluoroethanol • Recyclable perfluorinated solvent • 30 % H2O2 causes emulsions • Dihydroxylation • NaOAc increase yields Betzemeier, B.; Lhermitte, F.; Knochel, P. Synlett1999, 489. Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Seleniumand Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p 251-283.
Seleninic Acid Dihydroxylation Sheldon, R. A. et al. J. Chem. Soc., Perkin Trans. 12001, 224. Santoro, S.; Santi, C.; Sabatini, M.; Testaferri, L.; Tiecco, M. Adv. Synth. Catal. 2008, 350, 2881-2884.
Sequential Selenylation-Desenylation Santi, C. Et al. Chem. Eur. J. 2002, i, 1118. Freudendahl, D. M.; Santoro, S.; Shahzad, S. A.; Santi, C.; Wirth, T. Angew. Chem. Int. Ed. 2009, 48, 8409.
Sequential Selenylation-Desenylation Santi, C. Et al. Chem. Eur. J. 2002, i, 1118. Freudendahl, D. M.; Santoro, S.; Shahzad, S. A.; Santi, C.; Wirth, T. Angew. Chem. Int. Ed. 2009, 48, 8409.
Sequential Selenylation-Desenylation Santi, C. Et al. Chem. Eur. J. 2002, i, 1118. Freudendahl, D. M.; Santoro, S.; Shahzad, S. A.; Santi, C.; Wirth, T. Angew. Chem. Int. Ed. 2009, 48, 8409.
Alkyne Oxidation Santoro, S.; Battistelli, B.; Gjoka, B.; Si, C.-w. S.; Testaferri, L.; Tiecco, M.; Santi, C. Synlett, 2010, 1402.
Alkyne Oxidation Santoro, S.; Battistelli, B.; Gjoka, B.; Si, C.-w. S.; Testaferri, L.; Tiecco, M.; Santi, C. Synlett, 2010, 1402.
Alkyne Oxidation Santoro, S.; Battistelli, B.; Gjoka, B.; Si, C.-w. S.; Testaferri, L.; Tiecco, M.; Santi, C. Synlett, 2010, 1402.
Alcohol Oxidation van derToorn, J. C.; Kemperman, G.; Sheldon, R. A.; Arends, I. W. C. E. J. Org.Chem. 2009, 74, 3085.
Alcohol Oxidation • Excess of TBHP is to be avoided • Presence of water decrease the selectivity • Preactivation of the catalyst shortens reaction time van derToorn, J. C.; Kemperman, G.; Sheldon, R. A.; Arends, I. W. C. E. J. Org.Chem. 2009, 74, 3085.
Alcohol Oxidation van derToorn, J. C.; Kemperman, G.; Sheldon, R. A.; Arends, I. W. C. E. J. Org.Chem. 2009, 74, 3085.
Alcohol Oxidation Ehara, H.; Noguchi, M.; Sayama, S.; Onami, T. J. Chem. Soc., Perkin Trans. 12000, 1429.
Allylic Oxidation of Alkene Crich, D.; Zou, Y. Org. Lett. 2004, 6, 775-777.
Allylic Oxidation of Alkene • Iodoxybenzene (H2O2 less selective) • Electron-rich alkenes preferentially • Stable catalyst • Diselenide is recovered after Na2S2O5 quench(86 - 92%) Crich, D.; Zou, Y. Org. Lett. 2004, 6, 775-777.
Allylic Oxidation of Alkene • Oxidation on the more highly substituted side • Endocyclic oxidation for 1-substituted cyclohexene • krel: CH2 > CH3 > CH • Follows Bredt’s rule Crich, D.; Zou, Y. Org. Lett. 2004, 6, 775-777. Smith, M. B. Organic Synthesis; McGraw-Hill: Boston, MA, 2002; pp. 273-275.
Imine Oxidation, Catalytic Hydroxylation Brodsky, B. H.; Du Bois, J. J. Am. Chem. Soc.2005, 127, 15391.
Aniline Oxidation Priewisch, B.; Rück-Braun, K. J. Org. Chem. 2005, 70, 2350-2352. Zhao, D.; Johansson, M.; Bäckvall, J.-E. Eur. J. Org. Chem. 2007, 4431.
Oxidation of Bromide Salts • Br2, Br3+, HOBr • Seleninic acid electron rich reacts faster Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Seleniumand Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p 251-283.
Oxidation of Bromide Salts, Seleninic Acids • Unknown brominating species • Electron donating group acceleration Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Seleniumand Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p 251-283.
Oxidation of Bromide Salts, Selenoxide Goodman, M. A.; Detty, M. R. Organomet.2004, 23, 3016.
Oxidation of Bromide Salts, Seleninic Acid Drake, M. D.; Bateman, M. A.; Detty, M. R. Organomet. 2003, 22, 4158.
Disulfide Formation • Gluthathione peroxidase (GPx) • Selenoenzyme (L-selenocysteine) • Reactive oxygen species • Neurodegenerative disease (Parkinson, Alzheimer), physiological and inflammatory processes. • Chalcogen-based catalytic antioxidants Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Seleniumand Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p 251-283.
GPx Activity Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Seleniumand Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p 251-283.
Catlytic Reduction of Enones Tian, F.; Lu, S. Synlett 2004, 1953.
Catalytic Disulfide Formation Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Seleniumand Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p 251-283.
Diethyl Zinc Addition to Aldehydes Santi, C.; Wirth, T. Tetrahedron: Asym.1999, 10, 1019-1023. Wirth, T. Tetrahedron Lett.1995, 36, 7849-7852.
Diethyl Zinc Addition to Aldehydes Santi, C.; Wirth, T. Tetrahedron: Asym.1999, 10, 1019-1023. Wirth, T. Tetrahedron Lett.1995, 36, 7849-7852.
Diethyl Zinc Addition to Aldehydes Braga, A. L.; Galetto, F. Z.; Rodrigues, O. E. D.; Silveira, C. C.; Paixão, M. W. Chirality2008, 20, 839-845.
Diethyl Zinc Addition to Enones Shi, M.; Wang, C.-J.; Zhang, W. Chem. Eur. J. 2004, 10, 5507-5516.
Diethyl Zinc Addition to Enones Shi, M.; Wang, C.-J.; Zhang, W. Chem. Eur. J. 2004, 10, 5507-5516.
Malonate Alkylation Braga, A. L.; Galetto, F. Z.; Rodrigues, O. E. D.; Silveira, C. C.; Paixão, M. W. Chirality 2008, 20, 839.
Malonate Alkylation Braga, A. L.; Galetto, F. Z.; Rodrigues, O. E. D.; Silveira, C. C.; Paixão, M. W. Chirality 2008, 20, 839.
Conclusion • Selenium compounds are very versatile catalysts • Different oxidation state allows completely different reaction pathways • Little work as been focusing on their strong electron donating properties as a ligand • Little success in achieving stereoselective reactions with catalytic amount of enantioenriched organoselenium • Developpement towards its industrial use rather than fine chemistry