Enantioselective oxidations of sulfides catalyzed by chloroperoxidase

Abstract

The chloroperoxidase-catalyzed and horseradish peroxidase catalyzed oxidations of sulfides by tert-butyl and other peroxides have been investigated. The former metal enzyme afforded the corresponding sulfoxides having R absolute configuration in up to 92% enantiomeric excess (ee), whereas the latter gave racemic products. The various factors that control the enantioselectivity of the oxygenation have been examined.

Two-dimensional NMR Study of the Heme Active Site Structure of Chloroperoxidase

“…Furthermore, CPO has a unique ability to utilize halide (except fluoride) ions to halogenate a wide variety of organic acceptor molecules in the presence of hydrogen peroxide or other organic hydroperoxides (14 -16). Most importantly, CPO is adept in catalyzing the stereoselective epoxidation of alkenes (10,17,18), hydroxylation of alkynes (19,20), and oxidation of organic sulfides (21)(22)(23).…”

Enantioselective Epoxidation and Carbon–Carbon Bond Cleavage Catalyzed by Coprinus cinereus Peroxidase and Myeloperoxidase

“…In addition to one-electron oxidations and disproportionation of H 2 O 2 , peroxidases also catalyze oxygen transfer reactions, such as the formation of hypohalous acids from halide ions (2), the oxidation of indole to oxindole (3), the oxidation of amines to nitroso compounds (4), benzylic and propargylic hydroxylation (5,6), and the enantioselective sulfoxidation of sulfides have been reported (7)(8)(9)(10). Direct epoxidation of styrene and its derivatives, which is believed to be a difficult oxygen transfer process due to the higher redox potential of alkenes, has only been reported for CPO 1 from Caldariomyces fumago (11)(12)(13)(14)(15)(16)(17)(18)(19) and cytochrome c peroxidase (20).…”

Nuclear Magnetic Resonance Spectroscopic and Computational Investigations of Chloroperoxidase Catalyzed Regio- and Enantio-Selective Transformations

“…Significantly, the epoxidation and sulfoxidation reactions catalyzed by CPO are highly enantioselective [41,42,43,44,45,46,47], which suggests a potential application in pharmaceutical industry. …”

“…A remarkable feature of CPO is its ability to catalyze the enantioselective epoxidation of disubstituted alkenes [35,43], enantioselective oxidation of cis-cyclopropylmethanols [58], and asymmetry oxidation of sulfide [41,45]. There are several factors known to control the enantioselectivity such as steric effect, chain length, and electronic property of substituents.…”

“…The electronic property of substituents, that is activating or poorly group deactivating on the aromatic ring, can dramatically influence the outcome of CPO-catalyzed reactions [41]. For instance, the chemical yield and enantiomeric excess (ee) of para substitution, methyl p-tolyl sulfide, were reported higher than ortho substitution, methyl o-tolyl sulfide [41].…”