New Methodology for the Conversion of Epoxides to Alkenes

Wu, Feng‐Ling; Ross, Benjamin P.; McGeary, Ross P.

doi:10.1002/ejoc.200901264

Cited by 30 publications

(10 citation statements)

References 36 publications

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“…The employed synthetic protocol comprises of i) esterification, ii) epoxidation, iii) azidolysis, iv) "click" reaction followed by v) hydrolysis. According to Figure 1, the fatty acids 1/2/3 were converted to methyl esters 1a/2a/3a by treating with 2% H 2 SO 4 /MeOH 15 then subjected to epoxidation with m-CPBA in DCM 16 to obtain corresponding epoxy fatty acid methyl esters 1b/2b/3b in 85, 70 and 85% yield respectively.…”

Section: Results and Discussion: Chemistrymentioning

confidence: 99%

“…The residue obtained after removing the solvent in rotary evaporator under reduced pressure was purified by column chromatography (100% hexane) to afford pure fatty acid methyl ester. 16 (1b/2b/3b): A mixture of fatty acid methyl ester and m-CPBA (1:1.5) in DCM (20 mL) was stirred at room temperature for 4 h. The reaction mixture was washed with saturated solutions of NaHSO 3 followed by NaHCO 3 and NaCl. The organic layer was dried over anhydrous Na 2 SO 4 and the solvent was evaporated under reduced pressure.…”

Section: General Procedure: Synthesis Of Fatty Acid Methyl Ester 15 (mentioning

confidence: 99%

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2015

IJPSR

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A series of novel unsaturated fatty acid based hydroxy 1,2,3-triazole hybrids were designed and synthesised in excellent yields by esterification, epoxidation of oleic, ricinoleic and 10-undecenoic acids followed by azidolysis and "click" reaction with different alkynes. All the -hydroxy 1,2,3-triazole hybrids were characterised by ESI-MS, IR and NMR spectra as well as HRMS analysis and were screened in vitro for their anticancer activity against selected four human cancer cell lines (DU-145, HeLa, MCF-7 and A549) in comparison with doxorubicin, a standard anticancer drug. Among all the triazoles, methyl oleate with-CH 2 OH as 1,2,3-triazole side chain (1dii) exhibited good anti cancer activity against DU-145, HeLa, MCF-7 and A549 human cancer cell lines with IC 50 values 10.73, 13.61, 11.93, and 16.54 μM respectively.

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Section: Results and Discussion: Chemistrymentioning

confidence: 99%

Section: General Procedure: Synthesis Of Fatty Acid Methyl Ester 15 (mentioning

confidence: 99%

Untitled

2015

IJPSR

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“…By exploiting Togni reagent II as a source of CF 3 groups,23 12,12,12‐trifluorododecanoic acid ( 7 ) and 15,15,15‐trifluoropentadecanoic acid ( 8 ) were prepared by the efficient C(sp 3 )‐CF 3 bond‐forming reaction of Cu‐catalyzed trifluoromethylation of terminal olefins methyl 10‐undecenoate ( 18 )24 and methyl 13‐tetradecenoate ( 19 ) 25. The ester groups were unaffected under these mild conditions (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Regioselective Hydroxylation of C₁₂–C₁₅ Fatty Acids with Fluorinated Substituents by Cytochrome P450 BM3

Chiang¹,

Ramu²,

Tu³

et al. 2013

Chemistry A European J

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We demonstrate herein that wild-type cytochrome P450 BM3 can recognize non-natural substrates, such as fluorinated C12 -C15 chain-length fatty acids, and show better catalysis for their efficient conversion. Although the binding affinities for fluorinated substrates in the P450 BM3 pocket are marginally lower than those for non-fluorinated substrates, spin-shift measurements suggest that fluoro substituents at the ω-position can facilitate rearrangement of the dynamic structure of the bulk-water network within the hydrophobic pocket through a micro desolvation process to expel the water ligand of the heme iron that is present in the resting state. A lowering of the Michaelis-Menten constant (Km ), however, indicates that fluorinated fatty acids are indeed better substrates compared with their non-fluorinated counterparts. An enhancement of the turnover frequencies (kcat ) for electron transfer from NADPH to the heme iron and for CH bond oxidation by compound I (Cpd I) to yield the product suggests that the activation energies associated with going from the enzyme-substrate (ES state) to the corresponding transition state (ES(≠) state) are significantly lowered for both steps in the case of the fluorinated substrates. Delicate control of the regioselectivity by the fluorinated terminal methyl groups of the C12 -C15 fatty acids has been noted. Despite the fact that residues Arg47/Tyr51/Ser72 exert significant control over the hydroxylation of the subterminal carbon atoms toward the hydrocarbon tail, the fluorine substituent(s) at the ω-position affects the regioselective hydroxylation. For substrate hydroxylation, we have found that fluorinated lauric acids probably give a better structural fit for the heme pocket than fluorinated pentadecanoic acid, even though pentadecanoic acid is by far the best substrate among the reported fatty acids. Interestingly, 12-fluorododecanoic acid, with only one fluorine atom at the terminal methyl group, exhibits a comparable turnover frequency to that of pentadecanoic acid. Thus, fluorination of the terminal methyl group introduces additional interactions of the substrate within the hydrophobic pocket, which influence the electron transfers for both dioxygen activation and the controlled oxidation of aliphatics mediated by high-valent oxoferryl species.

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“…Spectroscopic data of compound 3c were identical to those described in the literature. 64 (2E,6E)-1-Benzyloxy-3,7,11-trimethyldodeca-2,6,10-triene (15c…”

Section: Synthesis Of the Substratesmentioning

confidence: 99%

Chemoselective and stereoselective lithium carbenoid mediated cyclopropanation of acyclic allylic alcohols

et al. 2016

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The reaction of geraniol with different lithium carbenoids generated from n-BuLi and the corresponding dihaloalkane has been evaluated. The reaction occurs in a chemo and stereoselective manner, which is consistent with a directing effect from the oxygen of the allylic moiety. Furthermore, a set of polyenes containing allylic hydroxyl or ether groups were chemoselectively and stereoselectively converted into the corresponding gem-dimethylcyclopropanes in one single step in moderate to good yields mediated by a lithium carbenoid generated in situ by the reaction of n-BuLi and 2,2-dibromopropane.

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New Methodology for the Conversion of Epoxides to Alkenes

Cited by 30 publications

References 36 publications

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Regioselective Hydroxylation of C₁₂–C₁₅ Fatty Acids with Fluorinated Substituents by Cytochrome P450 BM3

Chemoselective and stereoselective lithium carbenoid mediated cyclopropanation of acyclic allylic alcohols

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New Methodology for the Conversion of Epoxides to Alkenes

Cited by 30 publications

References 36 publications

Untitled

Untitled

Regioselective Hydroxylation of C12–C15 Fatty Acids with Fluorinated Substituents by Cytochrome P450 BM3

Chemoselective and stereoselective lithium carbenoid mediated cyclopropanation of acyclic allylic alcohols

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Regioselective Hydroxylation of C₁₂–C₁₅ Fatty Acids with Fluorinated Substituents by Cytochrome P450 BM3