4114-74-3Relevant articles and documents
A keto fatty acid from Smilax macrophylla seed oil
Daulatabad,Bhat,Jamkhandi
, p. 889 - 890 (1996)
A hitherto unknown keto fatty acid, 9-keto-octadec-cis-13-enoic acid, has been isolated from Smilax macrophylla seed oil in appreciable amounts (26.03%). Its identification was based on chemical and spectroscopic evidence.
A KETO FATTY ACID FROM LAGERSTROEMIA SPECIOSA SEED OIL
Jehan, Chirag Mahmood,Daulatabad, D.,Mirajkar, Abdurrazzaque M.
, p. 2323 - 2324 (1990)
A new keto fatty acid, (9-ketooctadec-cis-11-enoic acid), has been isolated from Lagerstroemia speciosa seed oil.Identification was made by chemical and spectroscopic methods.
A General Approach to Intermolecular Olefin Hydroacylation through Light-Induced HAT Initiation: An Efficient Synthesis of Long-Chain Aliphatic Ketones and Functionalized Fatty Acids
Guin, Joyram,Paul, Subhasis
supporting information, p. 4412 - 4419 (2021/02/05)
Herein, an operationally simple, environmentally benign and effective method for intermolecular radical hydroacylation of unactivated substrates by employing photo-induced hydrogen atom transfer (HAT) initiation is described. The use of commercially available and inexpensive photoinitiators (Ph2CO and NHPI) makes the process attractive. The olefin hydroacylation protocol applies to a wide array of substrates bearing numerous functional groups and many complex structural units. The reaction proves to be scalable (up to 5 g). Different functionalized fatty acids, petrochemicals and naturally occurring alkanes can be synthesized with this protocol. A radical chain mechanism is implicated in the process.
Saturated Oxo Fatty Acids (SOFAs): A Previously Unrecognized Class of Endogenous Bioactive Lipids Exhibiting a Cell Growth Inhibitory Activity
Batsika, Charikleia S.,Mantzourani, Christiana,Gkikas, Dimitrios,Kokotou, Maroula G.,Mountanea, Olga G.,Kokotos, Christoforos G.,Politis, Panagiotis K.,Kokotos, George
, p. 5654 - 5666 (2021/05/31)
The discovery of novel bioactive lipids that promote human health is of great importance. Combining suspect and targeted lipidomic liquid chromatography-high-resolution mass spectrometry (LC-HRMS) approaches, a previously unrecognized class of oxidized fatty acids, the saturated oxo fatty acids (SOFAs), which carry the oxo functionality at various positions of the long chain, was identified in human plasma. A library of SOFAs was constructed, applying a simple green photochemical hydroacylation reaction as the key synthetic step. The synthesized SOFAs were studied for their ability to inhibit in vitro the cell growth of three human cancer cell lines. Four oxostearic acids (OSAs) were identified to inhibit the cell growth of human lung carcinoma A549 cells. 6OSA and 7OSA exhibited the highest cell growth inhibitory potency, suppressing the expression of both STAT3 and c-myc, which are critical regulators of cell growth and proliferation. Thus, naturally occurring SOFAs may play a role in the protection of human health.
NMR-based molecular ruler for determining the depth of intercalants within the lipid bilayer. Part III: Studies on keto esters and acids
Afri, Michal,Alexenberg, Carmit,Aped, Pinchas,Bodner, Efrat,Cohen, Sarit,Ejgenburg, Michal,Eliyahu, Shlomi,Gilinsky-Sharon, Pessia,Harel, Yifat,Naqqash, Miriam E.,Porat, Hani,Ranz, Ayala,Frimer, Aryeh A.
, p. 105 - 118 (2015/02/19)
The development of "molecular rulers" would allow one to quantitatively locate the penetration depth of intercalants within lipid bilayers. To this end, an attempt was made to correlate the 13C NMR chemical shift of polarizable "reporter" carbons (e.g., carbonyls) of intercalants within DMPC liposomal bilayers - with the polarity it experiences, and with its Angstrom distance from the interface. This requires families of molecules with two "reporter carbons" separated by a known distance, residing at various depths/polarities within the bilayer. For this purpose, two homologous series of dicarbonyl compounds, methyl n-oxooctadecanoates and the corresponding n-oxooctadecanoic acids (n = 4-16), were synthesized. To assist in assignment and detection several homologs in each system were prepared 13C-enriched in both carbonyls. Within each family, the number of carbons and functional groups remains the same, with the only difference being the location of the second ketone carbonyl along the fatty acid chain. Surprisingly, the head groups within each family are not anchored near the lipid-water interface, nor are they even all located at the same depth. Nevertheless, using an iterative best fit analysis of the data points enables one to obtain an exponential curve. The latter gives substantial insight into the correlation between polarity (measured in terms of the Reichardt polarity parameter, ET(30)) and penetration depth into the liposomal bilayer. Still missing from this curve are data points in the moderate polarity range.
NMR-based molecular ruler for determining the depth of intercalants within the lipid bilayer. Part IV: Studies on ketophospholipids
Afri, Michal,Alexenberg, Carmit,Aped, Pinchas,Bodner, Efrat,Cohen, Sarit,Ejgenberg, Michal,Eliyahu, Shlomi,Gilinsky-Sharon, Pessia,Harel, Yifat,Naqqash, Miriam E.,Porat, Hani,Ranz, Ayala,Frimer, Aryeh A.
, p. 119 - 128 (2015/02/19)
In our companion paper, we described the preparation and intercalation of two homologous series of dicarbonyl compounds, methyl n-oxooctadecanoates and the corresponding n-oxooctadecanoic acids (n = 4-16), into DMPC liposomes. 13C NMR chemical shift of the various carbonyls was analyzed using an ET(30) solvent polarity-chemical shift correlation table and the corresponding calculated penetration depth (in A?). An iterative best fit analysis of the data points revealed an exponential correlation between ET(30) micropolarity and the penetration depth (in A?) into the liposomal bilayer. However, this study is still incomplete, since the plot lacks data points in the important area of moderately polarity, i.e., in the ET (30) range of 51- 45.5 kcal/mol. To correct this lacuna, a family of ketophospholipids was prepared in which the above n-oxooctadecanoic acids were attached to the sn-2 position of a phosphatidylcholine with a palmitic acid chain at sn-1. To assist in assignment and detection several derivatives were prepared 13C-enriched in both carbonyls. The various homologs were intercalated into DMPC liposomes and give points specifically in the missing area of the previous polarity-penetration correlation graph. Interestingly, the calculated exponential relationship of the complete graph was essentially the same as that calculated in the companion paper based on the methyl n-oxooctadecanoates and the corresponding n-oxooctadecanoic acids alone. The polarity at the midplane of such DMPC systems is ca. 33 kcal/mol and is not expected to change very much if we extend the lipid chains. This paper concludes with a chemical ruler that maps the changing polarity experienced by an intercalant as it penetrates the liposomal bilayer.
PROCESS FOR THE SYNTHESIS OF KETONES FROM INTERNAL ALKENES
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Page/Page column 0122; 0135; 0149, (2014/07/22)
The present invention is directed to methods for oxidizing internal olefins to ketones. In various embodiments, each method comprising contacting an organic substrate, having an initial internal olefin, with a mixture of (a) a biscationic palladium salt; and (b) an oxidizing agent; dissolved or dispersed in a solvent system to form a reaction mixture, said solvent system comprising at least one C2-6 carbon nitrile and optionally at least one secondary alkyl amide, said method conducted under conditions sufficient to convert at least 50 mol % of the initial internal olefin to a ketone, said ketone positioned on a carbon of the initial internal olefin. The transformation occurs at room temperature and shows wide substrate scope. Applications to the oxidation of seed oil derivatives and a bioactive natural product are described.
Steric analysis of epoxyalcohol and trihydroxy derivatives of 9-hydroperoxy-linoleic acid from hematin and enzymatic synthesis
Thomas, Christopher P.,Boeglin, William E.,Garcia-Diaz, Yoel,O'Donnell, Valerie B.,Brash, Alan R.
, p. 21 - 32 (2013/08/25)
We characterize the allylic epoxyalcohols and their trihydroxy hydrolysis products generated from 9R- and 9S-hydroperoxy-octadecenoic acid (HPODE) under non-enzymatic conditions, reaction with hematin and subsequent acid hydrolysis, and enzymatic conditions, incubation with Beta vulgaris containing a hydroperoxide isomerase and epoxide hydrolase. The products were resolved by HPLC and the regio and stereo-chemistry of the transformations were determined through a combination of 1H NMR and GC-MS analysis of dimethoxypropane derivatives. Four trihydroxy isomers were identified upon mild acid hydrolysis of 9S,10S-trans-epoxy-11E-13S-hydroxyoctadecenoate: 9S,10R,13S, 9S,12R,13S, 9S,10S,13S and 9S,12S,13S-trihydroxy-octadecenoic acids, in the ratio 40:26:22:12. We also identified a prominent δ-ketol rearrangement product from the hydrolysis as mainly the 9-hydroxy-10E-13-oxo isomer. Short incubation (5 min) of 9R- and 9S-HPODE with B. vulgaris extract yielded the 9R- and 9S-hydroxy-10E-12R,13S-cis-epoxy products respectively. Longer incubation (60 min) gave one specific hydrolysis product via epoxide hydrolase, the 9R/S,12S,13S-trihydroxyoctadecenoate. These studies provide a practical approach for the isolation and characterization of allylic epoxy alcohol and trihydroxy products using a combination of HPLC, GC-MS and 1H NMR.
Practical and general palladium-catalyzed synthesis of ketones from internal olefins
Morandi, Bill,Wickens, Zachary K.,Grubbs, Robert H.
supporting information, p. 2944 - 2948 (2013/04/10)
Make it simple! A convenient and general palladium-catalyzed oxidation of internal olefins to ketones is reported. The transformation occurs at room temperature and shows wide substrate scope. Applications to the oxidation of seed-oil derivatives and a bioactive natural product (see scheme) are described, as well as intriguing mechanistic features. Copyright
Anti-inflammatory constituents of the Red Alga Gracilaria verrucosa and their synthetic analogues
Hung, The Dang,Hye, Ja Lee,Eun, Sook Yoo,Shinde, Pramod B.,Yoon, Mi Lee,Hong, Jongki,Dong, Kyoo Kim,Jung, Jee H.
, p. 232 - 240 (2008/12/22)
A chemical study on the anti-inflammatory components of the red alga Gracilaria verrucosa led to the isolation of new 11-deoxyprostaglandins (1-4), a ceramide (5), and a C16 keto fatty acid (6), along with known oxygenated fatty acids (7-14). Their structures were elucidated on the basis of NMR and MS data. The absolute configurations of compounds 1-5 were determined by Mosher's method. The anti-inflammatory activity of the isolated compounds (1-14) was evaluated by determining their inhibitory effects on the production of pro-inflammatory mediators (NO, IL-6, and TNF-α) in lipopolysaccharide (LPS)-activated RAW 264.7 murine macrophage cells. Compounds 9 and 10 exhibited the most potent activity. In the evaluation of these two compounds and derivatized analogues (15-40), the anti-inflammatory activity was enhanced in some synthetic analogues. These enone fatty acids were investigated as potential anti-inflammatory leads for the first time.
