Abstract
AbstractKinetic resolution using biocatalysis has proven to be an excellent complementary technique to traditional asymmetric catalysis for the production of enantioenriched compounds. Resolution using oxidative enzymes produces valuable oxygenated structures for use in synthetic route development. This Minireview focuses on enzymes which catalyse the insertion of an oxygen atom into the substrate and, in so doing, can achieve oxidative kinetic resolution. The Baeyer–Villiger rearrangement, epoxidation, and hydroxylation are included, and biological advancements in enzyme development, and applications of these key enantioenriched intermediates in natural product synthesis are discussed.
Highlights
Kinetic resolution using biocatalysis has proven to be an excellent complementary technique to traditional asymmetric catalysis for the production of enantioenriched compounds
Resolution using oxidative enzymes produces valuable oxygenated structures for use in synthetic route development. This Minireview focuses on enzymes which cataexample, the use of alcohol dehydrogenases/ketoreductases),[4] or in which addition of oxygen occurs as a result of hydrolysis,[5] and enzymatic desymmetrisation[6] are outside of the scope of this lyse the insertion of an oxygen atom into the substrate and, in so doing, can achieve oxidative kinetic resolution
Expressing a sequence of alcohol dehydrogenase (ADH), enoate reductase (ERED), and Baeyer–Villiger monooxygenase (BVMO) in E. coli allowed the transformation of alcohol 10 through to the corresponding caprolactone 12 in 62 % overall yield and > 99 % ee
Summary
The flavin-dependent Baeyer–Villiger monooxygenase (BVMO) catalyses the oxidation of both cyclic and acyclic ketones to lactones and esters, respectively.[18]. Rudroff reported an in-depth substrate profiling for two new BVMOs: a camphor monooxygenase (CAMO) belonging to the CHMO subgroup and a 2-oxo-D3-4,5,5-trimethylcyclopentenyl-acetyl-coenzyme A monooxygenase (OTEMO).[27] Unsurprisingly, CAMO showed higher E values for a range of cyclohexanones; both enzymes gave generally poor selectivity with E = 3–69, apart from the substrate with R = Ph which gave E > 200 (Scheme 3) Both CAMO and OTEMO were shown to be excellent catalysts for the desymmetrisation of 3-vinylcyclobutanone and this led to the first chemoenzymatic synthesis of the Taniguchi lactone, a key intermediate in the synthesis of multiple natural products. The resulting selenoxides undergo belimination, yielding styrene-type structures as an unwanted side-product, leaving the unreacted (S)-selenide enantioenriched
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