Biocatalytic synthesis of C3 chiral building blocks by chloroperoxidase‐catalyzed enantioselective halo‐hydroxylation and epoxidation in the presence of ionic liquids

Abstract

The optically active C3 synthetic blocks are remarkably versatile intermediates for the synthesis of numerous pharmaceuticals and agrochemicals. This work provides a simple and efficient enzymatic synthetic route for the environment-friendly synthesis of C3 chiral building blocks. Chloroperoxidase (CPO)-catalyzed enantioselective halo-hydroxylation and epoxidation of chloropropene and allyl alcohol was employed to prepare C3 chiral building blocks in this work, including (R)-2,3-dichloro-1-propanol (DCP*), (R)-2,3-epoxy-1-propanol (GLD*), and (R)-3-chloro-1-2-propanediol (CPD*). The ee values of the formed C3 chiral building blocks DCP*, CPD*, and glycidol were 98.1, 97.5, and 96.7%, respectively. Moreover, the use of small amount of imidazolium ionic liquid enhanced the yield efficiently due to the increase of solubility of hydrophobic organic substrates in aqueous reaction media, as well as the improvement of affinity and selectivity of CPO to substrate.

How the Proximal Pocket May Influence the Enantiospecificities of Chloroperoxidase-Catalyzed Epoxidations of Olefins

“…Along with its native function of halogenating organic substrates using chloride, bromide and iodide ions [2,3,4], CPO is also capable of many promiscuous activities, including peroxidase, catalase and cytochrome P450 (P450) types of reactions [1]. CPO-catalyzed reactions are of biotechnological and environmental importance [5], therefore attracting current research interest on both the experimental [6,7,8,9,10,11,12,13,14] and theoretical sides [15,16,17,18,19,20,21]. The catalytic cycle requires a two-electron oxidation of the ferric heme center, using hydrogen peroxide or other suitable peroxide, and the glutamic acid side chain (E 183 ) in the distal pocket as a general acid-base catalyst, to form Compound I (CPO-I), a highly reactive oxyferryl porphyrin π-cation radical intermediate [15,20,22,23].…”

Ionic Liquids in Asymmetric Synthesis: An Overall View from Reaction Media to Supported Ionic Liquid Catalysis

“…Jiang and co-workers have introduced as imple and efficient enzymatic methodf or halohydroxylation and epoxidation of chloropropene and allyl alcohol by using ac hloroperoxidase (CPO) catalyst from Caldariomyces fumagois (a fungi). [73] The authors have synthesized three C 3 chiral buildingb locks [(R)-2,3dichloro-1-propanol,( R)-2,3-epoxy-1-propanol, and (R)-3chloro-1,2-propanediol],w hich are versatile intermediates for the synthesis of numerousp harmaceuticals, agrochemicals, perfumes, and liquid crystals. The yields of the products are not satisfactory in pure buffer solution, and thus, an ionic Scheme15.…”

Bienzymatic nanoreactors composed of chloroperoxidase–glucose oxidase on Au@Fe3O4 nanoparticles: Dependence of catalytic performance on the bioarchitecture

“…Chloroperoxidase (CPO), a heme-thiolate protein secreted by the marine fungus Caldariomyces fumago, is recognized as a versatile catalyst for various organic transformations including halogenation, Materials and Design 111 (2016) [414][415][416][417][418][419][420] oxidation, peroxidation, epoxidation and hydroxylation with high enantioselectivity [1][2][3][4]. However, the use of CPO in large-scale industrial applications is often handicapped by a lack of long-term operational stability, difficult recovery and the inability to be recycled [5].…”