Highly enantioselective epoxidation of disubstituted alkenes with hydrogen peroxide catalyzed by chloroperoxidase

Allain, E. J.; Hager, Lowell P.; Deng, Li; Jacobsen, Eric N.

doi:10.1021/ja00063a091

Cited by 240 publications

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“…The asymmetric epoxidation of styrenes also has received a considerable amount of interest. Various chiral catalysts and reagents have been investigated for the epoxidation of styrenes, including chiral porphyrin complexes (16 -34), chiral salen complexes (35)(36)(37)(38)(39)(40)(41)(42), chiral oxaziridines and oxaziridinium salts (43)(44)(45)(46), and enzymes (47)(48)(49)(50)(51). Metal catalysts such as chiral porphyrin and salen complexes have been studied extensively for the epoxidation of these alkenes, and the enantioselectivities have reached the 80% range in a number of cases (21,23,29,31,37,38,40,41), with 96% enantiomeric excess (ee) being obtained in one case (3,5-dinitrostyrene) (23).…”

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confidence: 99%

Highly enantioselective epoxidation of styrenes: Implication of an electronic effect on the competition between spiro and planar transition states

Hickey

Goeddel

Crane

et al. 2004

Proc. Natl. Acad. Sci. U.S.A.

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Asymmetric epoxidation of various styrenes using carbocyclic oxazolidinone-containing ketone 3 has been investigated. High enantioselectivity (89 -93% enantiomeric excess) has been attained for this challenging class of alkenes. Mechanistic studies show that substituents on the ketone catalyst can have electronic influences on secondary orbital interactions, which affects the competition between spiro and planar transition states and, ultimately, enantioselectivity. The results described herein not only reveal the potential of chiral dioxirane catalyzed asymmetric epoxidation as a viable entry into this important class of olefins but also further enhance the understanding of the mechanistic aspects of chiral ketone-catalyzed asymmetric epoxidation. Epoxides are important intermediates for the synthesis of complex molecules. Asymmetric epoxidation of prochiral alkenes presents a powerful strategy for the synthesis of enantiomerically enriched epoxides. Great progress has been made in the areas of asymmetric epoxidation of allylic alcohols (1-3), chiral metal complex-catalyzed epoxidation of unfunctionalized alkenes (particularly with conjugated cis-and trisubstituted alkenes) (4 -7), and asymmetric epoxidation of electron-deficient alkenes under nucleophilic conditions (8 -10). Styrene oxides are extremely useful and can be prepared by a number of methods such as asymmetric reduction of ␣-halo acetophenones (refs. 11 and 12 and references therein), asymmetric dihydroxylation of styrenes (13,14), and kinetic resolution of racemic epoxides (15). The asymmetric epoxidation of styrenes also has received a considerable amount of interest. Various chiral catalysts and reagents have been investigated for the epoxidation of styrenes, including chiral porphyrin complexes (16 -34), chiral salen complexes (35-42), chiral oxaziridines and oxaziridinium salts (43-46), and enzymes (47-51). Metal catalysts such as chiral porphyrin and salen complexes have been studied extensively for the epoxidation of these alkenes, and the enantioselectivities have reached the 80% range in a number of cases (21,23,29,31,37,38,40,41), with 96% enantiomeric excess (ee) being obtained in one case (3,5-dinitrostyrene) (23).Among other oxidants, dioxiranes either isolated or generated in situ are powerful epoxidation agents (Scheme 1; refs. 52-54). Chiral dioxiranes were shown recently to be effective for asymmetric epoxidation of trans-, trisubstituted (55-91), and certain cis-alkenes (92-95). Asymmetric epoxidation of styrenes with chiral dioxiranes has been studied also (61,66,68,81,88,90,(93)(94)(95); however, the enantioselectivity has not exceeded 85% (93-95). Generally speaking, the highly enantioselective epoxidation of styrenes still remains a formidable challenge.During our studies, we found that varying the catalyst structure could have a dramatic effect on enantioselectivity for the dioxirane-mediated epoxidation of styrene. Fructosederived ketone 1 (Scheme 2), a very effective catalyst for transand trisubstituted alkenes, gave only 24...

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confidence: 99%

Highly enantioselective epoxidation of styrenes: Implication of an electronic effect on the competition between spiro and planar transition states

Hickey

Goeddel

Crane

et al. 2004

Proc. Natl. Acad. Sci. U.S.A.

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“…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).…”

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

Wang

Tachikawa

et al. 2003

Journal of Biological Chemistry

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“…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). The active site in CPO contains a distal glutamate and a proximal cysteine, whereas in classical peroxidases both a distal and a proximal histidine are present (21).…”

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confidence: 99%

“…As side products, unsubstituted phenylacetaldehydes are formed (11,13,16). Very high enantioselectivities are obtained with disubstituted olefins (12,14).…”

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confidence: 99%

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

Tuynman¹,

Spelberg²,

Kooter³

et al. 2000

Journal of Biological Chemistry

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We demonstrate that myeloperoxidase (MPO) and Coprinus cinereus peroxidase (CiP) catalyze the enantioselective epoxidation of styrene and a number of substituted derivatives with a reasonable enantiomeric excess (up to 80%) and in a moderate yield. Three major differences with respect to the chloroperoxidase from Caldariomyces fumago (CPO) are observed in the reactivity of MPO and CiP toward styrene derivatives. First, in contrast to CPO, MPO and CiP produced the (S)-isomers of the epoxides in enantiomeric excess. Second, for MPO and CiP the H 2 O 2 had to be added very slowly (10 eq in 16 h) to prevent accumulation of catalytically inactive enzyme intermediates. Under these conditions, CPO hardly showed any epoxidizing activity; only with a high influx of H 2 O 2 (300 eq in 1.6 h) was epoxidation observed. Third, both MPO and CiP formed significant amounts of (substituted) benzaldehydes as side products as a consequence of C-␣-C-␤ bond cleavage of the styrene derivatives, whereas for CPO and cytochrome c peroxidase this activity is not observed. C-␣-C-␤ cleavage was the most prominent reaction catalyzed by CiP, whereas with MPO the relative amount of epoxide formed was higher. This is the first report of peroxidases catalyzing both epoxidation reactions and carboncarbon bond cleavage. The results are discussed in terms of mechanisms involving ferryl oxygen transfer and electron transfer, respectively.

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Highly enantioselective epoxidation of disubstituted alkenes with hydrogen peroxide catalyzed by chloroperoxidase

Cited by 240 publications

References 0 publications

Highly enantioselective epoxidation of styrenes: Implication of an electronic effect on the competition between spiro and planar transition states

Highly enantioselective epoxidation of styrenes: Implication of an electronic effect on the competition between spiro and planar transition states

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

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

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