Designing new chiral ketone catalysts. Asymmetric epoxidation of cis-olefins and terminal olefins

This paper describes a new class of chiral oxazolidinone ketone catalyst for asymmetric epoxidation. High ee values have been obtained for a number of cyclic and acyclic cis-olefins. The epoxidation was stereospecific with no isomerization observed in the epoxidation of acyclic systems. Encouragingly high ee values have also been obtained for a number of terminal olefins. Mechanistic studies show that electronic interactions play an important role in stereodifferentiation.     

Remarkable enhancement of aerobic epoxidation reactivity for olefins catalyzed by μ-oxo-bisiron(III) porphyrins under ambient conditions

With μ-oxo dimeric iron(III) porphyrins [(Fe^IIITPP)₂O] as catalyst, isobutylaldehyde as co-reductant, and dioxygen as oxidant, an efficient model system for epoxidation of olefins has been developed. Compared with mono-metalloporphyrins as catalyst, a remarkable enhancement of reactivity was obtained for the present olefin epoxidation system, in which the turnover number (TON) of the catalyst has doubled from about 700 million to 1400 million. Moreover, a plausible mechanism involving both binuclear and mononuclear intermediate has been proposed.     

A cyclodextrin-modified ketoester for stereoselective epoxidation of alkenes

A beta-cyclodextrin-modified ketoester 2 was prepared by covalent attachment of a reactive ketone moiety to beta-cyclodextrin. Treatment of 2 with Oxone as terminal oxidant would produce CD-substituted dioxirane, which can effect stereoselective alkene epoxidation. The 2-mediated (S)-alpha-terpineol epoxidations proceeded to give terpineol oxides in high yields, and the stereoselectivities (i.e., cis-/trans-epoxide ratio) decreased from 2.5:1 to 1:1.2 with increasing steric bulkiness of the terpenes. This steric-dependent stereoselectivity can be understood based on different binding geometries of the 2/terpene inclusion complexes according to the (1)H NMR titration and 2D ROESY experiments. Enantioselective epoxidation of styrenes has also been achieved with 2 as catalyst (20-50 mol %) in aqueous acetonitrile solution, and up to 40% ee was obtained in 4-chlorostyrene epoxidation at 0 degrees C. Similar enantioselectivities were also obtained for the 2-mediated epoxidation of 1,2-dihydronaphthalene (37% ee), 4-chlorostyrene (36% ee), and trans-stilbene (31% ee).     

Highly enantioselective epoxidation of alpha,beta-unsaturated esters by chiral dioxirane

This paper describes a highly enantioselective epoxidation of alpha,beta-unsaturated esters using the fructose-derived ketone 2 as catalyst and Oxone as oxidant. High ee's have been obtained for a number of trans and trisubstituted substrates (82-98% ee). The results described show that it is feasible for dioxiranes to effectively epoxidize electron-deficient olefins with high ee's.     

Lipase-catalyzed kinetic resolution of cyclic trans-1,2-diols bearing a diester moiety: synthetic application to chiral seven-membered-ring alpha,alpha-disubstituted alpha-amino acid

Chiral cycloalkane-trans-1,2-diols (+/-)-3 and (+/-)-8 having a diester moiety have been prepared from dimethyl dialkenylmalonate using olefin metathesis by Grubbs catalyst, followed by epoxidation and acidic hydrolysis. Kinetic resolution of racemic cyclopentane-trans-1,2-diol (+/-)-3 by lipase-catalyzed transesterification afforded an optically active monoacetate (-)-5 of 95% ee in 46% yield and the recovered diol (-)-3 of 92% ee in 51% yield, and that of cycloheptane-trans-1,2-diol (+/-)-8 gave a monoacetate (+)-10 of 95% ee in 51% yield and the diol (-)-8 of >99% ee in 43% yield, respectively. The enantiomer selectivity of racemic cyclic trans-1,2-diols bearing a diester moiety by lipases (Amano PS and Amano AK) was opposite to that of the reported simple racemic cycloalkane-trans-1,2-diols. To explain the lipase-catalyzed enantiomer selectivity, computer modeling of lipase-substrate complexes was performed. Furthermore, the optically active diester (-)-8 could be efficiently converted into an optically active seven-membered-ring alpha,alpha-disubstituted amino acid (4R,5R)-(-)-15.     

Recent Advances in Facile Liquid Phase Epoxidation of Light Olefins over Heterogeneous Molybdenum Catalysts

Molybdenum complexes are versatile and efficient for liquid phase olefin epoxidation reactions. Rational design of catalysts is critical to achieve high atom efficiency during epoxidation processes. Although liquid phase epoxidation has been a popular topic for decades, three key issues, (a) rational control of morphology of molybdenum nanoparticles, (b) manipulating metal‐support interaction and (c) altering electronic configuration at molybdenum center remains unsolved in this area. Therefore, in this paper, we have critically revised recent research progress on heterogeneous molybdenum catalysts for facile liquid phase olefin epoxidation in terms of catalyst synthesis, surface characterization, catalytic performance and structure‐function relationship. Furthermore, plausible reaction mechanisms will be systematically discussed with the aim to provide insights into fundamental understanding on novel epoxidation chemistry.     

An N-aryl-substituted oxazolidinone-containing ketone-catalyzed asymmetric epoxidation with hydrogen peroxide as the primary oxidant

Asymmetric epoxidation of various olefins with an N-aryl-substituted oxazolidinone-containing ketone as catalyst and hydrogen peroxide as the primary oxidant has been investigated, and up to 96% ee was obtained.     

High enantioselectivities in an (E)-alkene epoxidation by catalytically active chromium salen complexes. Insight into the catalytic cycle

[structure: see text]. The epoxidation of (E)-beta-methylstyrene mediated by an oxochromium salen complex yields the epoxide in 92% ee in stoichiometric mode, the highest ee yet reported for a metal-mediated epoxidation of an (E)-alkene. The effect of added donor ligands, previously substantial, has reached a ceiling with this complex. In catalytic mode a slightly reduced ee and higher yield is obtained, indicating both the presence of a second oxidation cycle and that the major oxidant reacts with its reduced form.     

Organocatalytic stereoselective epoxidation of trisubstituted acrylonitriles

The first diastereospecific and enantioselective epoxidation of trans-2-aroyl-3-arylacrylonitriles by means of the commercially available diaryl L-prolinol/tert-butyl hydroperoxide system has been developed. These diversely functionalized epoxides were obtained in excellent yield (up to 99%), complete diastereoselectivity for the trans-isomer, and good enantioselectivity (up to 84% ee). Highly enantioenriched epoxides can be easily obtained after a single crystallization (ee > 90%).     

Effective asymmetric epoxidation of styrenes by chiral dioxirane

High enantioselectivity (80-92% enantiomeric excess (ee)) has been obtained for the epoxidation of various styrenes using an easily prepared ketone (4) catalyst.     

Asymmetric epoxidation catalyzed by N-aryl-substituted oxazolidinone-containing ketones: further evidence for electronic effects

[reaction: see text] Ketones containing N-aryl-substituted oxazolidinones have been prepared and investigated for the epoxidation of cis-beta-methylstyrene, styrene, and 1-phenylcyclohexene. The attractive interaction between the phenyl group of the olefin and the oxazolidinone of the catalyst is enhanced by introducing an electron-withdrawing group onto the N-phenyl group of the catalyst. The information obtained gives a better understanding of the ketone-catalyzed epoxidation. In addition, the easy preparation of some of the ketones makes them good candidates for practical use.     

Iminium salt catalysts for asymmetric epoxidation: the first high enantioselectivities

A highly enantioselective iminium salt catalyst has been prepared and tested in the catalytic asymmetric epoxidation of unfunctionalized alkenes, giving up to 95% ee, the highest ee yet reported for iminium salt-catalyzed epoxidation. Catalyst loadings as low as 0.1 mol % may be used.     

Synthesis of a new chiral N,N,N-tridentate pyridinebisimidazoline ligand library and its application in Ru-catalyzed asymmetric epoxidation

A small ligand library of chiral tridentate N,N,N-pyridinebisimidazolines have been synthesized for the first time. This new class of ligands can be easily tuned and synthesized on multi g-scale. The usefulness of the ligands is shown in the ruthenium-catalyzed asymmetric epoxidation with hydrogen peroxide as oxidant. Excellent yields (>99%) and good enantioselectivities (up to 71% ee) have been obtained for the epoxidation of aromatic olefins. [reaction: see text]     

beta-peptides as catalysts: poly-beta-leucine as a catalyst for the Juliá-Colonna asymmetric epoxidation of enones

Poly-beta-leucines have been evaluated as catalysts for the Juliá-Colonna asymmetric epoxidation of enones; the beta 3-isomer was found to be an effective catalyst for the epoxidation of chalcone (70% ee) and some analogues.     

Enantioselective epoxidation of terminal olefins by chiral dioxirane

[see reaction]. This paper describes an enantioselective epoxidation of terminal olefins using chiral ketone 3 as catalyst and Oxone as oxidant. Up to 85% ee has been obtained.     

Effective and recyclable dendritic ligands for the enantioselective epoxidation of enones

An operationally simple and mild protocol for the catalytic enantioselective epoxidation of enones has been established using a series of chiral pyrrolidinylmethanol-based dendritic catalysts and tert-butyl hydroperoxide (TBHP) as an oxidant. The epoxides have been obtained in good yields and ee up to 78%.     

Mechanism of olefin epoxidation with transition metal peroxo complexes: DFT study

Using density functional calculations over the last decade led to considerable progress in understanding the mechanism of olefin epoxidation with Ti, V, Mo, W, and Re peroxo complexes. According to calculations, the reaction occurs by direct electrophilic transfer of one of the atoms of the peroxo group to the olefin. The alternative stepwise mechanism, which has been discussed for a long time and suggested the formation of a metallocyclic intermediate, is characterized by higher activation barriers than direct transfer. The electrophilic character of the direct transfer of oxygen was interpreted at the level of molecular orbital analysis as interaction between the HOMO of the olefin π(C-C) and the LUMO of the peroxo group σ*(O-O). The factors determining the activity of various metal complexes in epoxidation were examined in relation to the ligand environment and the structure of the peroxo group.     

Enantioselective epoxidation of alpha,beta-enones promoted by alpha,alpha-diphenyl-L-prolinol as bifunctional organocatalyst

[reaction: see text] An operationally simple and mild protocol for the catalytic enantioselective epoxidation of alpha,beta-unsaturated ketones has been estabilished using commercially available alpha,alpha-diphenyl-l-prolinol as bifunctional organocatalyst and tert-butyl hydroperoxide (TBHP) as oxidant. The epoxides have been obtained in good yields and with up to 80% ee.     

Asymmetric epoxidation of 6-cyano-2,2-dimethylchromene on Mn(salen) catalyst immobilized in mesoporous materials

This article reports our recent work on the heterogeneous asymmetric epoxidation catalyzed by chiral Mn(salen) catalyst axially immobilized via phenoxyl groups and organic sulfonic groups. The asymmetric epoxidation of 6-cyano-2,2-dimethylchromene was especially presented in detail. The factors that affected the asymmetric induction, such as the nanopores and the external surface, the linkage length, and the modification of nanopores with methyl groups were discussed. It was found that the enantioselectivities increased with decreasing the nanopore sizes or increasing the linkage length in nanopore, and the Mn(salen) catalyst immobilized into nanopores generally gave higher ee values than those on the external surface. The heterogeneous Mn(salen) catalysts with modified nanopores gave a TOF of 14.8 h⁻¹ and an ee value of 90.6% for the asymmetric epoxidation of 6-cyano-2,2-dimethylchromene, which were higher than the results (TOF 10.8 h⁻¹, ee 80.1%) obtained for the homogeneous catalyst.     

Synthesis and Application of Novel Chiral Poly-nuclear-Mn(Ⅲ) Catalysts on Asymmetric Epoxidation of Alkenes

The interest of the coordination chemistry of manganese has been driver by the important roles of metalloenzymes and highly valuable catalysts in olefin expoxidation.1 Jacobsen Salen-Mn complexes with a simple structure have been commercially utilized to catalyze asymmetric epoxidation of unfunctionalized cis-alkenes2, but the catalytic enantioselectivity for trans-alkenes, unfortunately, are lower and this kinds of complexes are unstable and difficult to be recovered for reuse.3 In order to improve the catalytic activity and recyclability, many new catalysts including the supported catalysts,heterogeneous catalysts and else modified catalysts have been studied, however their comprehensive effects are unsatisfying.4Recently, some studies in interrelated realm showed that the catalytic performance of bi- or poly-nuclear complexes was superior to that of monomer.5 Meanwhile, our previous studies also showed that properly increasing the molecular weight of catalysts as well as the extent of conjugation of active center would not only result in high activity or reactivity but also its stability and recyclablity, aiding product isolation and catalyst recovery.6For these reasons we designed and synthesized the chiral poly-Mn(Ⅲ) complexes in which active sites were conjugated in certain distance side by side though central nucleus of 4, 6-dihydroxy- isophthalaldehyde (see the scheme). These novel Mn(Ⅲ) complexes have been investigated for the first time as catalysts (lmol%)for the asymmetric epoxidation of alkenes by using pure urea-H2O2 as oxidant and NH4OAc as additive in CH2Cl2/MeOH, showing high activity and good enantioselectivity. All reactions were finished in 1.5h. Rather surprisingly, a marginal increase in ee was observed when the concentration of the substrate was increased from 0.01 to 0.5M. The poly-nuclear complex formation enhanced the catalyst's reactivity and stability. It, unlike mononuclear, could be easily recovered and reused several cycles with a decline of yield but a keep of ee's.A low concentration requirement of catalyst, high ee and chemical activity, mild reaction conditions and catalytic recycles render the kinds of complexes attractive.