Ferric Perchlorate: An Efficient Reagent for Regio- and Stereoselective Alcoholysis and Hydrolysis of Epoxides

Three‐Membered Heterocycles. Structure and Reactivity

“…The conversion of epoxides into diols in this manner is the basis for an enormously important method for preparing optically pure epoxides from racemic mixtures through hydrolytic kinetic resolution (HKR) [578]. Chiral nonracemic diols are also available from the hydrolytic desymmetrization of meso-epoxides (e.g., 440) using an oligomeric Jacobsen-type catalyst (530) [579].…”

“…The electrophilic center is cleanly inverted in the process [581]. This addition can also be carried out using ferric perchlorate [579], molybdenum(VI) dichloride dioxide [582], hydrazine sulfate [583], amberlyst-15 resin [584], copper(II) tetrafluoroborate [585], and aminopropylsilica gel (APSG) supported iodine [586]. The hydroperoxide anion functions as a competent nucleophile under the catalysis of silica-supported antimony trichloride [587].…”

“…For example, phenyloxymethyl epoxide 532 (Scheme 2.96) is converted into the corresponding episulfide in excellent yield under these conditions (Table 2.19) [690]. Very good yields have been reported using potassium thiocyanate in a biphasic medium of ionic liquid and water with no additional catalyst [579]. Finally, elemental sulfur can be employed as the donor using diethylphosphite, ammonium acetate and alumina in the absence of solvent under microwave irradiation.…”

Ferric Perchlorate Catalyzed One‐pot Synthesis of 1,2,3,4‐Tetrahydro‐2‐pyrimidinones and ‐thiones: an Expedient Protocol for the Biginelli Reaction

“…The oxidation potential of ferric perchlorate in methanol is only 0.70 eV. 8 Recently we have reported the ability of ferric perchlorate as a catalyst for alcoholysis and hydrolysis of epoxide, 9 transetherification of allylic and benzylic ethers, 10 aromatization of Hantzsh 1,4-dihydropyridines 11 and tetrahydropyranylation of alcohols and deprotection of THP ethers. 12 We have also recently reported on the catalytic activity of natural heulandite 13 and 12-tungstophosphoric acid 14 in Biginelli reaction.…”

Functionalization of epoxy esters with alcohols as stoichiometric reagents

“…Regioselectivity of the addition can be influenced somewhat by the use of metal salts (Li, Mg, Zn) as catalysts. 7 In more recent times a number of Lewis acid catalysts, based on mostly transition metals was introduced, including copper(II) tetrafluoroborate, 8 iron(III) perchlorate, 9 titanium compounds, 10 aluminum triflate 11 and others.…”