Oxidation with Peroxides
Peroxide Oxidations:
Novel Organic Peroxygen Reagents for use in Organic Synthesis,
Heaney, H. Top. Curr. Chem. 1993, 164, 1.
Enantioselective Epoxidation with Peroxidic Oxygen,
Höft, E. Top. Curr. Chem. 1993, 164, 63.
Organic Peroxides,
Ando, W., Wiley: Chichester, U.K., 1992.
Oxidation Reactions Using Magnesium Monoperphthalate and Urea Hydrogen Peroxide,
Heaney, H. Aldrichimica Acta 1993, 26, 35.
Catalytic Oxidations with Hydrogen Peroxide as Oxidant,
Strukul, G., Ed. Kluwer, 1992.
The Mechanism of the Directing of Functional Groups and the Geometry of Reactant Molecules on the Peroxide Epoxidation of Alkenes,
Dryuk, V. G.; Kartsev, V. G. Russ. Chem. Rev. 1999, 68, 206-26.
Organic Synthesis Utilizing Tetrabutylammonium Peroxydisulfate,
Kim, Y. H.; Yang, S. G. Rev. Heteroatom Chem. 1999, 20, 69-96.
Hydroxy Group Directivity in the Epoxidation of Chiral Allylic Alcohols: Control of Diastereoselectivity through Allylic Strain and Hydrogen Bonding,
Adam, W.; Wirth, T. Acc. Chem. Res. 1999, 32, 703-10.
Metal-Catalyzed Epoxidations of Alkenes with Hydrogen Peroxide,
Lane, B. S.; Burgess, K. Chem. Rev. 2003, 103, 2457-73.
Oxidation with Hydrogen Peroxide and tButyl Hydroperoxide
Hydrogen peroxide is a general purpose oxidant. The inherent reactivity is not very high, so it is commonly used with acid, base or transition metal catalysts which provide more aggressive nucleophilic or eletrophilic oxidants. It is also used to prepare peracids and other peroxy compounds
Ouabain Model: Jung, M. E.; Piizzi, G. Org. Lett. 2003, 5, 137
Pancratistatin-Deoxy: Acena, J. L.; Arjona, O.; Leon, L.; Plumet, J. Org. Lett. 2000, 2, 3683-3686.
Sharpless Epoxidation
Asymmetric Epoxidation of Allylic Alcohols: The Katsuki-Sharpless Epoxidation Reaction,
Katsuki, T.; Martin, V. S. Org. React. 1996, 48, 1-299.
The most important hydroperoxide epoxidation is the titanium catalyzed asymmetric epoxidation of allyl alcohols for which Sharpless won the Nobel Prize in 2001. This reaction requires an allylic alcohol group, which coordinates to the titanium during the reaction. The active oxidant is t-butyl hydroperoxide. The ditheyl tartrate also coordinates to the titanium and creates a chiral environment for the oxygen transfer. Isolated double bonds are not oxidized.
Nobel-Prize-winning chemistry
K. B. Sharpless, 2001
Cerulenin: Mani, N. S.; Townsend, C. A. J. Org. Chem. 1997, 62, 636
Here an asymmetric epoxidation is used to perform an asymmetric Markovnikov hydration of the allyl alcohol double bond. Neither the other double bond nor the triple bond is affected. Deacetoxyalcyonin Acetate: MacMillan, D. W. C.; Overman, L. E. J. Am. Chem. Soc. 1995, 117, 10391.
