Carl Trudel, Literature Meeting Wednesday, April 11 th 2012

Singh, F. V.; Wirth, T. In Organoselenium Chemistry; Wiley-VCH Verlag GmbH & Co. KGaA, 2012, p Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Selenium and Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p About this presentation

3 About Me

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 4

Fun Facts Discovered by J. J. Berzelius in 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!) 5 Berzelius, J. J. Afhandl. Fys. Kemi Mineralogi. 1818, 42. Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Selenium and Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p [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) $/mol SeO $/mol Ph 2 Se $/mol (PhSe) ,29 $/mol [mCPBA $/mol] 6 www. sigmaaldrich.com [april 2012]

Soichiometric Selenium Chemistry 7 Reich, H. J.; Cohen, M. L.; Clark, P. S. Org. Synth. 1988, 50-9, Santi, C.; Wirth, T. Tetrahedron: Asymm. 1999, 10, Thompson, D. P.; Boudjouk, P. J. Org. Chem. 1988, 53,

Carbonylation of aminoalcohols 8 1 st Selenium Catalyzed Reaction Sonoda, N.; Yamamoto, G.; Natsukawa, K.; Kondo, K.; Murai, S. Tetrahedron Lett. 1975, 16,

Perseleninic acid Hydroxy Perhydroxy Selenane 9 Selenium Based Oxygen Transfer Reagents Davis, F. A.; Reddy, R. T. J. Org. Chem. 1992, 57,

10 Baeyer-Villiger Reaction Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Selenium and Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p

11 Baeyer-Villiger Reaction, Perseleninic Acids Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Selenium and Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p

12 Catalytic Baeyer-Villiger Reaction Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Selenium and Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p

13 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.

C3° > C2° > Bn > Ar/H* > C1° > Me CF 3 CH 2 OH, 20 °C Hydrolysis might be an issue Important substituent effect 14 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.

Pioneer work by Sharpless 15 Seleninic Acid Epoxidation Hori, T.; Sharpless, K. B. J. Org. Chem. 1978, 43,

Pioneer work by Sharpless 16 Seleninic Acid Epoxidation Hori, T.; Sharpless, K. B. J. Org. Chem. 1978, 43,

DCM or trifluoroethanol Recyclable perfluorinated solvent 30 % H 2 O 2 causes emulsions Dihydroxylation NaOAc increase yields 17 Seleninic Acid Epoxidation Betzemeier, B.; Lhermitte, F.; Knochel, P. Synlett 1999, 489. Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Selenium and Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p

18 Seleninic Acid Dihydroxylation Santoro, S.; Santi, C.; Sabatini, M.; Testaferri, L.; Tiecco, M. Adv. Synth. Catal. 2008, 350, Sheldon, R. A. et al. J. Chem. Soc., Perkin Trans , 224.

19 Sequential Selenylation-Desenylation Santi, C. Et al. Chem. Eur. J. 2002, i, Freudendahl, D. M.; Santoro, S.; Shahzad, S. A.; Santi, C.; Wirth, T. Angew. Chem. Int. Ed. 2009, 48, 8409.

20 Sequential Selenylation-Desenylation Santi, C. Et al. Chem. Eur. J. 2002, i, Freudendahl, D. M.; Santoro, S.; Shahzad, S. A.; Santi, C.; Wirth, T. Angew. Chem. Int. Ed. 2009, 48, 8409.

21 Sequential Selenylation-Desenylation Santi, C. Et al. Chem. Eur. J. 2002, i, Freudendahl, D. M.; Santoro, S.; Shahzad, S. A.; Santi, C.; Wirth, T. Angew. Chem. Int. Ed. 2009, 48, 8409.

22 Alkyne Oxidation Santoro, S.; Battistelli, B.; Gjoka, B.; Si, C.-w. S.; Testaferri, L.; Tiecco, M.; Santi, C. Synlett, 2010, 1402.

23 Alkyne Oxidation Santoro, S.; Battistelli, B.; Gjoka, B.; Si, C.-w. S.; Testaferri, L.; Tiecco, M.; Santi, C. Synlett, 2010, 1402.

24 Alkyne Oxidation Santoro, S.; Battistelli, B.; Gjoka, B.; Si, C.-w. S.; Testaferri, L.; Tiecco, M.; Santi, C. Synlett, 2010, 1402.

25 Alcohol Oxidation van der Toorn, J. C.; Kemperman, G.; Sheldon, R. A.; Arends, I. W. C. E. J. Org.Chem. 2009, 74, 3085.

Excess of TBHP is to be avoided Presence of water decrease the selectivity Preactivation of the catalyst shortens reaction time 26 Alcohol Oxidation van der Toorn, J. C.; Kemperman, G.; Sheldon, R. A.; Arends, I. W. C. E. J. Org.Chem. 2009, 74, 3085.

27 Alcohol Oxidation van der Toorn, J. C.; Kemperman, G.; Sheldon, R. A.; Arends, I. W. C. E. J. Org.Chem. 2009, 74, 3085.

28 Alcohol Oxidation Ehara, H.; Noguchi, M.; Sayama, S.; Onami, T. J. Chem. Soc., Perkin Trans , 1429.

29 Allylic Oxidation of Alkene Crich, D.; Zou, Y. Org. Lett. 2004, 6,

Iodoxybenzene (H 2 O 2 less selective) Electron-rich alkenes preferentially Stable catalyst Diselenide is recovered after Na 2 S 2 O 5 quench( %) 30 Allylic Oxidation of Alkene Crich, D.; Zou, Y. Org. Lett. 2004, 6,

31 Allylic Oxidation of Alkene Crich, D.; Zou, Y. Org. Lett. 2004, 6, Smith, M. B. Organic Synthesis; McGraw-Hill: Boston, MA, 2002; pp Oxidation on the more highly substituted side Endocyclic oxidation for 1-substituted cyclohexene k rel : CH2 > CH3 > CH Follows Bredt’s rule

32 Imine Oxidation, Catalytic Hydroxylation Brodsky, B. H.; Du Bois, J. J. Am. Chem. Soc. 2005, 127,

33 Aniline Oxidation Priewisch, B.; Rück-Braun, K. J. Org. Chem. 2005, 70, Zhao, D.; Johansson, M.; Bäckvall, J.-E. Eur. J. Org. Chem. 2007, 4431.

Br 2, Br 3 +, HOBr Seleninic acid electron rich reacts faster 34 Oxidation of Bromide Salts Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Selenium and Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p

Unknown brominating species Electron donating group acceleration 35 Oxidation of Bromide Salts, Seleninic Acids Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Selenium and Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p

36 Oxidation of Bromide Salts, Selenoxide Goodman, M. A.; Detty, M. R. Organomet. 2004, 23, 3016.

37 Oxidation of Bromide Salts, Seleninic Acid Drake, M. D.; Bateman, M. A.; Detty, M. R. Organomet. 2003, 22, 4158.

Gluthathione peroxidase (GPx) Selenoenzyme (L-selenocysteine) Reactive oxygen species Neurodegenerative disease (Parkinson, Alzheimer), physiological and inflammatory processes. Chalcogen-based catalytic antioxidants 38 Disulfide Formation Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Selenium and Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p

39 GPx Activity Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Selenium and Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p

40 Catlytic Reduction of Enones Tian, F.; Lu, S. Synlett 2004, 1953.

41 Catalytic Disulfide Formation Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Selenium and Tellurium Chemistry; Springer Berlin Heidelberg, 2011, p

Diethyl Zinc Addition to Aldehydes 42 Santi, C.; Wirth, T. Tetrahedron: Asym. 1999, 10, Wirth, T. Tetrahedron Lett. 1995, 36,

Diethyl Zinc Addition to Aldehydes 43 Santi, C.; Wirth, T. Tetrahedron: Asym. 1999, 10, Wirth, T. Tetrahedron Lett. 1995, 36,

Diethyl Zinc Addition to Aldehydes 44 Braga, A. L.; Galetto, F. Z.; Rodrigues, O. E. D.; Silveira, C. C.; Paixão, M. W. Chirality 2008, 20,

Diethyl Zinc Addition to Enones 45 Shi, M.; Wang, C.-J.; Zhang, W. Chem. Eur. J. 2004, 10,

Diethyl Zinc Addition to Enones 46 Shi, M.; Wang, C.-J.; Zhang, W. Chem. Eur. J. 2004, 10,

Malonate Alkylation 47 Braga, A. L.; Galetto, F. Z.; Rodrigues, O. E. D.; Silveira, C. C.; Paixão, M. W. Chirality 2008, 20, 839.

Malonate Alkylation 48 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 49