Nickel-catalyzed cycloaddition of anthranilic acid derivatives to alkynes

A nickel-catalyzed cycloaddition has been developed where readily available anthranilic acid derivatives react with alkynes to afford substituted indoles. The reaction involves oxidative addition of Ni(0) to an ester moiety, which allows intermolecular addition to alkynes via decarbonylation and 1,3-acyl migration.     

Decarbonylative cycloaddition of phthalic anhydrides with allenes

The decarbonylative cycloadditions of phthalic anhydrides with allenes were performed by using nickel catalyst. The asymmetric variant of the cycloaddition was also achieved by using chiral phosphine ligands to provide δ-lactones enantioselectively.     

Dehydrogenative Diels-Alder reaction

The dehydrogenative cycloaddition of dieneynes, which possess a diene in the form of a styrene moiety and a dienophile in the form of an alkyne moiety, produces naphthalene derivatives when heated. It was found that a key requirement of this process is the presence of a silyl group attached to the alkyne moiety, which forces a dehydrogenation reaction to occur.     

Development of a polar lipid profiling method by supercritical fluid chromatography/mass spectrometry

We established a high-throughput and high-resolution analytical method based on supercritical fluid chromatography (SFC) coupled with mass spectrometry (MS) for the simultaneous profiling of diverse polar lipids in a mixture. Trimethylsilyl (TMS) derivatization was used for the analysis of ten polar lipids: phosphatidylglycerol (PG), phosphatidic acid (PA), phosphatidylinositol (PI), lysophosphatidylcholine (LPC), lysophosphatidylethanolamine (LPE), lysophosphatidylglycerol (LPG), lysophosphatidic acid (LPA), lysophosphatidylinositol (LPI), sphingomyeline (SM), and sphingosine-1-phosphate (S1P). Using the developed method, the peak tailings of PA, PI, LPA, LPI, and S1P improved, and the limit of detection of PG, PI, LPA, LPI, and S1P was enhanced by 12-, 40-, 510-, 39-, and 1490-fold, respectively. Next, in the analysis of sheep plasma, 20 minor species of PI, LPC, LPE, and SM, and 7 molecular species of LPA, LPI, and S1P were additionally analyzed. The relative ratio of the molecular species in each polar lipid was also found by quantification. Finally, the simultaneous and detail profiling of ten polar lipids was successfully performed by SFC/MS applying TMS derivatization. This developed method is particularly applicable to metabolomics, especially for targeting polar lipids.     

Specific counterion effect on the adsorbed film of cationic surfactant mixtures at the air/water interface

To investigate the counterion effects, we employed dodecyltrimethylammonium bromide (DTABr)-dodecyltrimethylammonium tetrafluoroborate (DTABF(4)) mixed aqueous solutions and measured their surface tensions, then analyzed these data in a thermodynamic treatment. The tensiometry showed that DTABF(4) was more effective in lowering the surface tension of water. The phase diagram of adsorption demonstrated that the surface was enriched with BF(4)(-) ions, but the composition of Br(-) ions in the adsorbed film was slightly enhanced compared to the ideal mixing criteria. These were explained in terms of the size and polarizability of counterions. Moreover, the distribution of counterions of the DTABr-DTABF(4) mixtures in the adsorbed film is greatly different from that of the 1-hexyl-3-methylimidazolium bromide (HMIMBr)-1-hexyl-3-methylimidazolium tetrafluoroborate (HMIMBF(4)) mixtures, where a stronger hydrogen-bonding exists between BF(4)(-) and HMIM(+) ions. These findings suggest that the adsorption of counterions in electric double layers is likely subject to two factors: the nature of counterion and their interactions with surfactant ions.     

Nickel-catalyzed intermolecular codimerization of acrylates and alkynes

The linear codimerization of acrylates and alkynes to produce 1,3-dienes is successfully demonstrated using a nickel catalyst in association with 2-aminopyridine as an additive.     

Nickel-iminophosphine-catalyzed [4+2] cycloaddition of enones with allenes: synthesis of highly substituted dihydropyrans

Enones were found to react with allenes intermolecularly in the presence of a catalytic amount of a nickel-iminophosphine complex to provide dihydropyrans via oxidative cyclization of an enone and Ni(0).     

Control of the Solid‐State Chiral Optical Properties of a Supramolecular Organic Fluorophore Containing 4‐(2‐Arylethynyl)‐Benzoic Acid

The solid‐state chiral optical properties of a 4‐(2‐arylethynyl)‐benzoic acid/amine supramolecular organic fluorophore can be controlled by changing the arylethynyl group of the achiral 4‐(2‐arylethynyl)‐benzoic acid component molecule rather than the chirality of the amine component molecule.