Selenium and Tellurium Chemistry
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Transcript Selenium and Tellurium Chemistry
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.
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About Me
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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
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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. 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 285-302.
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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]
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www. sigmaaldrich.com [april 2012]
Soichiometric Selenium Chemistry
Reich, H. J.; Cohen, M. L.; Clark, P. S. Org.
Synth. 1988, 50-9, 533-537.
Thompson, D. P.; Boudjouk, P. J. Org. Chem.
1988, 53, 2109-2112.
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Santi, C.; Wirth, T. Tetrahedron: Asymm. 1999, 10, 1019-1023.
1st Selenium Catalyzed Reaction
Carbonylation
of aminoalcohols
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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
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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 Selenium and Tellurium Chemistry; Springer
Berlin Heidelberg, 2011, p 251-283.
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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 251-283.
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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 251-283.
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Catalytic Baeyer-Villiger Reaction
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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
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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
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Hori, T.; Sharpless, K. B. J. Org. Chem. 1978, 43, 1689-1697.
Seleninic Acid Epoxidation
Pioneer work by Sharpless
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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. Synlett 1999, 489.
Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Selenium and Tellurium Chemistry; Springer Berlin 17
Heidelberg, 2011, p 251-283.
Seleninic Acid Dihydroxylation
Sheldon, R. A. et al. J. Chem. Soc., Perkin Trans. 1 2001, 224.
Santoro, S.; Santi, C.; Sabatini, M.; Testaferri, L.; Tiecco, M. Adv.
Synth. Catal. 2008, 350, 2881-2884.
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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.
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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.
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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.
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Alkyne Oxidation
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Santoro, S.; Battistelli, B.; Gjoka, B.; Si, C.-w. S.; Testaferri, L.; Tiecco, M.; Santi, C. Synlett, 2010, 1402.
Alkyne Oxidation
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Santoro, S.; Battistelli, B.; Gjoka, B.; Si, C.-w. S.; Testaferri, L.; Tiecco, M.; Santi, C. Synlett, 2010, 1402.
Alkyne Oxidation
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Santoro, S.; Battistelli, B.; Gjoka, B.; Si, C.-w. S.; Testaferri, L.; Tiecco, M.; Santi, C. Synlett, 2010, 1402.
Alcohol Oxidation
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van der Toorn, 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 der Toorn, J. C.; Kemperman, G.; Sheldon, R. A.; Arends, I. W. C. E. J. Org.Chem. 2009, 74, 3085.
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Alcohol Oxidation
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van der Toorn, J. C.; Kemperman, G.; Sheldon, R. A.; Arends, I. W. C. E. J. Org.Chem. 2009, 74, 3085.
Alcohol Oxidation
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Ehara, H.; Noguchi, M.; Sayama, S.; Onami, T. J. Chem. Soc., Perkin Trans. 1 2000, 1429.
Allylic Oxidation of Alkene
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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%)
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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.
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Imine Oxidation, Catalytic Hydroxylation
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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.
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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 Selenium and Tellurium Chemistry; Springer
Berlin Heidelberg, 2011, p 251-283.
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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 Selenium and Tellurium Chemistry; Springer
Berlin Heidelberg, 2011, p 251-283.
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Oxidation of Bromide Salts, Selenoxide
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Goodman, M. A.; Detty, M. R. Organomet. 2004, 23, 3016.
Oxidation of Bromide Salts, Seleninic Acid
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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 Selenium and Tellurium Chemistry; Springer
Berlin Heidelberg, 2011, p 251-283.
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GPx Activity
Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Selenium and Tellurium Chemistry; Springer
Berlin Heidelberg, 2011, p 251-283.
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Catlytic Reduction of Enones
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Tian, F.; Lu, S. Synlett 2004, 1953.
Catalytic Disulfide Formation
Alberto, E. E.; Braga, A. L.; Woollins, J. D.; Laitinen, R. In Selenium and Tellurium Chemistry; Springer
Berlin Heidelberg, 2011, p 251-283.
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Diethyl Zinc Addition to Aldehydes
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Santi, C.; Wirth, T. Tetrahedron: Asym. 1999, 10, 1019-1023. Wirth, T. Tetrahedron Lett. 1995, 36, 7849-7852.
Diethyl Zinc Addition to Aldehydes
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Santi, C.; Wirth, T. Tetrahedron: Asym. 1999, 10, 1019-1023. Wirth, T. Tetrahedron Lett. 1995, 36, 7849-7852.
Diethyl Zinc Addition to Aldehydes
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Braga, A. L.; Galetto, F. Z.; Rodrigues, O. E. D.; Silveira, C. C.; Paixão, M. W. Chirality 2008, 20, 839-845.
Diethyl Zinc Addition to Enones
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Shi, M.; Wang, C.-J.; Zhang, W. Chem. Eur. J. 2004, 10, 5507-5516.
Diethyl Zinc Addition to Enones
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Shi, M.; Wang, C.-J.; Zhang, W. Chem. Eur. J. 2004, 10, 5507-5516.
Malonate Alkylation
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Braga, A. L.; Galetto, F. Z.; Rodrigues, O. E. D.; Silveira, C. C.; Paixão, M. W. Chirality 2008, 20, 839.
Malonate Alkylation
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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
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