67663-02-9

Usage

InChI:InChI=1/C6H12O2/c1-2-5-6(8-5)3-4-7/h5-7H,2-4H2,1H3

Upstream product

• 928-96-1 (Z)-3-Hexen-1-ol 
• 928-97-2 (E)-3-hexen-1-ol 
• 78947-94-1 3-(1-iodoprop-1-yl)-2,6-dioxacyclohexanone 
• 544-12-7 3-hexen-1-ol 

Downstream Products

• 16432-53-4 hexane-1,4-diol 
• 21531-91-9 1,3-hexanediol 
• 795280-56-7 rac-N-benzyl-2-((2R,3S)-3-ethyloxiran-2-yl)ethan-1-amine 

Relevant academic research and scientific papers

Mo Schiff base-tungstate ionic hybrid with enhanced heterogeneous catalytic activity for epoxidation reactions

A novel metal Schiff base-tungstate ionic hybrid (Mo-MimAM-WO4) was prepared by anion-exchange of Mo Schiff base functionalized imidazole ionic liquid with sodium tungstate. The resulting hybrid catalyst was fully characterized by 1H NMR, FT-IR, XRD, SEM, TGA, and XPS, and its catalytic activity was studied for the epoxidation of alkenes using aqueous H2O2 as the oxidant. The catalyst was found to be highly efficient and showed higher catalytic activity than its corresponding homogeneous and heterogeneous analogues Mo-MimAM and Na2WO4. After reaction, the catalyst can be easily recovered by filtration and reused for the next run. The synergistic effect between Mo Schiff base complex and tungstate is revealed to be responsible for the catalyst's excellent performance in epoxidation.

Highly Regioselective 5-endo-tet Cyclization of 3,4-Epoxy Amines into 3-Hydroxypyrrolidines Catalyzed by La(OTf)3

Highly regioselective intramolecular aminolysis of 3,4-epoxy amines has been achieved. Key features of this reaction are (1) chemoselective activation of epoxides in the presence of unprotected aliphatic amines in the same molecules by a La(OTf)3 catalyst and (2) excellent regioselectivity for anti-Baldwin 5-endo-tet cyclization. This reaction affords 3-hydroxy-2-alkylpyrrolidines stereospecifically in high yields. DFT calculations revealed that the regioselectivity might be attributed to distortion energies of epoxy amine substrates. The use of this reaction was demonstrated by the first enantioselective synthesis of an antispasmodic agent prifinium bromide.

New heptacoordinate tungsten(II) complexes with α-diimine ligands in the catalytic oxidation of multifunctional olefins

New tungsten(II) and molybdenum(II) heptacoordinate complexes [MX2(CO)3(LY)] (MXLy: M = W, Mo; X = Br, I; LY = C5H4NCY = N(CH2)2CH3 with Y = H (L1), Me (L2), Ph (L3)) were synthesized and characterized by spectroscopic techniques and elemental analysis. The two tungsten complexes WXL1 (X = Br, I) were also structurally characterized by single crystal X-ray diffraction. The metal coordination environment is in both a distorted capped octahedron. The complexes with L1 and L2 ligands were grafted in MCM-41, after functionalization of the ligands with a Si(OEt)3 group. The new materials were characterized by elemental analysis, N2 adsorption isotherms, 29Si MAS and 13C MAS NMR. The tungsten(II) complexes and materials were the first examples of this type reported. All complexes and materials were tested as homogeneous and heterogeneous catalysts in the oxidation of multifunctional olefins (cis-hex-3-en-1-ol, trans-hex-3-en-1-ol, geraniol, S-limonene, and 1-octene), with tert-butyl hydroperoxide (TBHP) as oxidant. The molybdenum(II) catalyst precursors are in general very active, reaching 99% conversion and 100% selectivity in the epoxidation of trans-hex-3-en-1-ol. Their performance is comparable with that of the [Mo(η3-C3H5)X(CO)2(LY)] complexes, but it increases with immobilization. On the other hand, most of the W(II) complexes display an activity similar or inferior to that of the Mo(II) analogues and it decreases after they are supported in MCM-41. DFT calculations show that tungsten complexes and iodide ligands are more easily oxidized from M(II) to M(VI) than molybdenum ones, while the energies of relevant species in the catalytic cycle are very similar for all complexes, making the theoretical rationalization of experimental catalytic data difficult.

New molybdenum(II) complexes with α-diimine ligands: Synthesis, structure, and catalytic activity in olefin epoxidation

Three new complexes [Mo(η3-C3H5)Br(CO)2{iPrN=C(R)C5H4N}], where R = H (IMP = N-isopropyl 2-iminomethylpyridine), Me, and Ph, were synthesized and characterized, and were fluxional in solution. The most interesting feature was the presence, in the crystal structure of the IMP derivative, of the two main isomers (allyl and carbonyls exo), namely the equatorial isomer with the Br trans to the allyl and the equatorial with the Br trans to one carbonyl, the position trans to the allyl being occupied by the imine nitrogen atom. For the R = Me complex, the less common axial isomer was observed in the crystal. These complexes were immobilized in MCM-41 (MCM), following functionalization of the diimine ligands with Si(OEt)3, in order to study the catalytic activity in olefin epoxidation of similar complexes as homogeneous and heterogeneous catalysts. FTIR,13C- and29Si-NMR, elemental analysis, and adsorption isotherms showed that the complexes were covalently bound to the MCM walls. The epoxidation activity was very good in both catalysts for the cis-cyclooctene and cis-hex-3-en-1-ol, but modest for the other substrates tested, and no relevant differences were found between the complexes and the Mo-containing materials as catalysts.

Synthesis and catalytic activity of Mo(II) complexes of α-diimines intercalated in layered double hydroxides

The two layered double hydroxides ZnAl-LDH and MgAl-LDH were functionalized with bis(4-HOOC-phenyl)-acenaphthenequinonediimine) (H2BIAN), leading to the intercalation of its dianion, which in a second step reacted with [Mo(CO)3X2(NCMe)2] (X = I, Br), affording four new materials. These materials and the two complexes [Mo(CO)3X2(H2BIAN)2] (X = I, Br) were tested in the olefin epoxidation reaction with substrates cis-cyclooctene, styrene, 1-octene, trans-hex-3-en-1-ol, and R-(+)-limonene, using tert-butylhydroperoxide (tbhp) as oxidant. The new catalysts were particularly good for cis-cyclooctene and styrene (100% conversions) and at least one heterogeneous catalyst was comparable to the homogeneous ones in the epoxidation of 1-octene and trans-hex-3-en-1-ol. The homogeneous catalysts were the best to oxidize R-(+)-limonene (higher conversions).

Characterization of Carbonyl-Phenol Adducts Produced by Food Phenolic Trapping of 4-Hydroxy-2-hexenal and 4-Hydroxy-2-nonenal

4-Hydroxy-2-alkenals disappear in the presence of food phenolics (i.e., cathechin or quercetin), and the corresponding carbonyl-phenol adducts are produced. In an attempt to identify structure(s) of formed adducts, the reactions between model phenolics (resorcinol, 2-methylresorcinol, orcinol, and 2,5-dimethylresorcinol) and hydroxyalkenals (4-hydroxy-2-hexenal and 4-hydroxy-2-nonenal) were studied and the produced adducts were isolated by column chromatography and unambiguously characterized by one- A nd two-dimensional nuclear magnetic resonance and mass spectrometry as dihydrobenzofuranols (1), chromane-2,7-diols (2), and 2H-chromen-7-ols (3). These compounds were mainly produced at slightly basic pH values and moderate temperatures. Their activation energies (Ea) of formation were a25 kJ mol-1 for adducts 1, a32 kJ mol-1 for adducts 2, and a38 kJ mol-1 for adducts 3. A reaction pathway that explains their formation is proposed. All of these results confirm that, analogously to other lipid-derived carbonyl compounds, phenolics can trap 4-hydroxy-2-alkenals in an efficient way. Obtained results provide the basis for the potential detection of carbonyl-phenol adducts derived from hydroxyalkenals in food products.

Asymmetric Total Synthesis of 19,20-Epoxydocosapentaenoic Acid, a Bioactive Metabolite of Docosahexaenoic Acid

In this study, we report the first asymmetric total synthesis of 19,20-epoxydocosapentaenoic acid (19,20-EDP), a naturally occurring bioactive cytochrome P450 metabolite of docosahexaenoic acid, a major constituent of fish oil. Our strategy involves direct asymmetric epoxidation to produce an enantiopure β-epoxyaldehyde that can be appended to the rest of the skipped polyene core by Wittig condensation. Our route is step-economical and late divergent and could be an appealing method by which to synthesize EDP analogues for biological studies.

Molybdenum(II) Complexes with α-Diimines: Catalytic Activity in Organic and Ionic Liquid Solvents

The new [MoX(η3-C3H5)(CO)2(α-diimine)] complexes with: (i) X = Br or triflate and α-diimine = 1,10-phenanthroline (phen) and dipyridophenazine (dppz); and (ii) X = Br and α-diimine = phen and dppz, with several substituents, are synthesized and characterized. The structures of [MoBr(η3-C3H5)(CO)2(Cl-phen)] and [Mo(CF3SO3)(η3-C3H5)(CO)2(dppz)] are determined by using single-crystal X-ray diffraction. These and three complexes of 2,2′-bipyridyl (bpy), and its two derivatives with Me and tBu substituents, are tested in the homogeneous catalytic epoxidation of several olefins in dichloromethane, exhibiting, in general, a good selectivity towards the respective epoxide and relatively low TOFs. For the first time, the oxidation of cis-cyclooctene with some of these catalysts is also conducted in a variety of room-temperature ionic liquids (RTILs). In the presence of [MoBr(η3-C3H5)(CO)2(phen)], the conversions, in general, increase, compared with the reactions in organic solvents. Interestingly, different chemoselectivity is found when [C6mim][Ntf2] and [C2mim][FAP] are used with diol (24–26 %). On the other hand, [MoBr(η3-C3H5)(CO)2(L)] (L = Me-phen or dppz) exhibits much lower conversions in the RTILs tested than in common organic solvents.

Borinic Acid-Catalyzed, Regioselective Ring Opening of 3,4-Epoxy Alcohols

Diarylborinic acids (Ar2BOH) catalyze the C3-selective ring opening of 3,4-epoxy alcohols with aniline, dialkylamine and arenethiol nucleophiles. The regiochemical outcome is consistent with a catalytic tethering mechanism in which the borinic acid interacts with both the electrophile and the nucleophile. The rate acceleration resulting from this induced intramolecularity effect is sufficient to overcome steric biases that would otherwise favor C4-selective opening of the substituted epoxy alcohols.

An Isolable and Bench-Stable Epoxidizing Reagent Based on Triazine: Triazox

A new triazine-based oxidizing reagent, 2-hydroperoxy-4,6-diphenyl-1,3,5-triazine (Triazox), has been developed. The reagent can be synthesized from inexpensive starting materials and is a bench-stable solid that is isolable in pure form. Epoxidation of alkenes possessing acid-sensitive functionalities using Triazox proceeded in good to excellent yields. The accompanying nonacidic triazinone coproduct can be easily removed by filtration. These features indicate that Triazox is a practically useful oxidizing reagent.