Peroxy Acids and Esters
Examples: meta-chloroperbenzoic acid, peracetic acid, trifluoroacetic peracid, phthaloyl peroxide, tert-butyl peroxybenzoate, see also: peroxides
Sodium percarbonate allows the convenient preparation of peroxy acids from acid chlorides, and even from the acids themselves.
Recent Literature
Anhydrous [2-percarboxyethyl] functionalized silica is an advantageous
oxidant for epoxidation of olefins. The acidic silica surface does not catalyze
ring-opening reactions except for particularly activated styrene oxide. Alkenes
carrying hydroxyl groups react with silica-supported peracid faster than
unsubstituted alkenes. Products can be isolated after simple filtration and
solvent evaporation.
R. Mello, A. Alcalde-Aragonés, M. E. González Núńez, G. Asensio, J. Org. Chem., 2012,
77, 6409-6413.
Addition of perfluoro-tert-butyl alcohol to a toluene solution of
alkene and cyclopropyl malonoyl peroxide increases the rate of dihydroxylation
product formation and the stereoselectivity observed, providing a simple and
effective method for acceleration of this important class of reaction. Basic
hydrolysis of the crude reaction mixture provides access to syn-diols in
high yield and stereoselectivity.
S. Picon, M. Rawling, M. Campbell, N. C. O. Tomkinson, Org. Lett., 2012,
14, 6250-6253.
The use of nonanebis(peroxoic acid) enables a regio- and chemoselective
oxidation of aromatic amines hindered with an ortho substituent to the
corresponding nitro compounds, except for anilines ortho-substituted with
amino groups (NH2, NHR) or hydroxyl groups, where H-bonding between
an hydrogen of the adjacent group and an oxygen atom from the diperoxy acid
directs the oxidation.
V. V. Patil, G. S. Shankarling, J. Org. Chem.,
2015,
80, 7876-7883.
The oxidation of malononitrile derivatives with peracid in methanol proceeds
with loss of the cyano groups to yield methyl esters in high yield. The method
was applied to a variety of malononitrile derivatives, some of which were
prepared by Pd- or Ir-catalyzed asymmetric allylic substitution.
S. Förster, O. Tverskoy, G. Helmchen, Synlett, 2008,
2803-2806.
