Peroxide oxidation of primary alcohols to aldehydes by chloroperoxidase catalysis

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

“…CPO is able to catalyze a wide variety of reactions including halogenation [28,29,30], oxidation [31,32,33,34,35,36], N-demethylation [37,38], dehalogenation [39,40], and dismutation reactions [31] (see Figure 1.6). 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.…”

“…The substrates of CPO oxidation include a wide variety of organic compounds such as indole [33,55], monoterpenes [56], 4-chloroaniline (to 4-chloronitrosobenzene) [32], and the classical peroxidase substrates such as guaiacol, pyrogallol, and leucomalachite green [31]. In particular, the primary alcohols can be selectively oxidized to aldehyde in the presence of CPO and hydrogen peroxide (H 2 O 2 ) [34].…”

“…The speed at which the oxidant is added affects the yield of CPO-catalyzed oxidation, as the sensitivity of CPO for hydrogen peroxide has to be taken into account [34]. For instance, oxidation of 5-hydroxymethylfurfural was shown to approach completion only when the H 2 O 2 was added slowly.…”

“…To overcome this restriction, one way is to perform the reaction in aqueous co-solvent mixtures [121]. However, common solvents such as methanol [34] and dimethylsulfoxide [122] are both reported to be the substrates of CPO. Van Deurzen et al reported that tert-butanol/water (50:50, v/v) could be a good solvent system [121], which could increase the solubility of the organic compound and maintain most of the CPO activity.…”

“…Chloroperoxidase (CPO), a heme-thiolate protein secreted by the marine fungus Caldariomyces fumago [23], is a versatile enzyme [25] capable of catalyzing a broad spectrum of chemical reactions including halogenation [28], dehalogenation [39], N-demethylation [37], dismutation [23], epoxidation [42], and oxidation [34,41,129,130,131]. Therefore, CPO has been the subject of numerous biotechnological investigations due to its potential applications in synthetic chemistry as well as pharmaceutical industry [44,46,132,133].…”