Studies on the syntheses of heterocyclic compounds. part CDLV. The mass spectral investigation and synthesis of the ochotensinan skeleton

Syntheses of several 1-spiroisoquinoline derivatives (VIII, IX, X, XI, XII, XIII, and XIV) were carried out and their unique mass spectral fragmentations were reported. The presence of carbonyl groups at the C-9 and C-14 positions caused cleavage of the five membered ring through the elimination of one or two carbon monoxide groups. This led to the formation of the three membered ring system on the fragmentation pathway.     

Donor–acceptor–acceptor-type near-infrared fluorophores that contain dithienophosphole oxide and boryl groups: effect of the boryl group on the nonradiative decay

The use of donor–π–acceptor (D–π–A) skeletons is an effective strategy for the design of fluorophores with red-shifted emission. In particular, the use of amino and boryl moieties as the electron-donating and -accepting groups, respectively, can produce dyes that exhibit high fluorescence and solvatochromism. Herein, we introduce a dithienophosphole P-oxide scaffold as an acceptor–spacer to produce a boryl- and amino-substituted donor–acceptor–acceptor (D–A–A) π-system. The thus obtained fluorophores exhibit emission in the near-infrared (NIR) region, while maintaining high fluorescence quantum yields even in polar solvents (e.g. λ_em = 704 nm and Φ_F = 0.69 in CH₃CN). A comparison of these compounds with their formyl- or cyano-substituted counterparts demonstrated the importance of the boryl group for generating intense emission. The differences among these electron-accepting substituents were examined in detail using theoretical calculations, which revealed the crucial role of the boryl group in lowering the nonradiative decay rate constant by decreasing the non-adiabatic coupling in the internal conversion process. The D–A–A framework was further fine-tuned to improve the photostability. One of these D–A–A dyes was successfully used in bioimaging to visualize the blood vessels of Japanese medaka larvae and mouse brain.

Combination of electron-accepting diarylboryl terminal groups and dithienophosphole oxide spacers with electron-donating triarylamine moieties produces donor–acceptor–acceptor type π-systems, which exhibit emissions in the near-infrared region.     

Novel 2-pyrone synthesis via the nucleophilic addition of active methine compounds to 2-alkynone

Novel 2-pyrone synthesis via the nucleophilic addition of active methine compounds to 2-alkynone has been developed. The reaction of active methine compounds with 2-alkynone provided 2-pyrones in good yields.     

Nucleic acid related compounds. 116. Nonaqueous diazotization of aminopurine nucleosides. Mechanistic considerations and efficient procedures with tert-butyl nitrite or sodium nitrite

Nonaqueous diazotization-dediazoniation of two types of aminopurine nucleoside derivatives has been investigated. Treatment of 9-(2,3,5-tri-O-acetyl-beta-D-ribofuranosyl)-2-amino-6-chloropurine (1) with SbCl(3)/CH(2)Cl(2) was examined with benzyltriethylammonium (BTEA) chloride as a soluble halide source and tert-butyl nitrite (TBN) or sodium nitrite as the diazotization reagent. Optimized yields (>80%) of the 2,6-dichloropurine derivative were obtained with SbCl(3). Combinations with SbBr(3)/CH(2)Br(2) gave the 2-bromo-6-chloropurine product (>60%), and SbI(3)/CH(2)I(2)/THF gave the 2-iodo-6-chloropurine derivative (>45%). Antimony trihalide catalysis was highly beneficial. Mixed combinations (SbX(3)/CH(2)X'(2); X/X' = Br/Cl) gave mixtures of 2-(bromo, chloro, and hydro)-6-chloropurine derivatives that were dependent on reaction conditions. Addition of iodoacetic acid (IAA) resulted in diversion of purine radical species into a 2-iodo-6-chloropurine derivative with commensurate loss of other radical-derived products. This allowed evaluation of the efficiency of SbX(3)-promoted cation-derived dediazoniations relative to radical-derived reactions. Efficient conversions of adenosine, 2'-deoxyadenosine, and related adenine nucleosides into 6-halopurine derivatives of current interest were developed with analogous combinations.     

Inhibition of prostaglandin and leukotriene biosynthesis by gingerols and diarylheptanoids.

The rhizomes of Zingiber officinale (ginger) and Alpinia officinarum contain potent inhibitors against prostaglandin biosynthesizing enzyme (PG synthetase). Gingerols and diarylhepatanoids were identified as active compounds. Their possible mechanism of action which was deduced from the structures of active compounds indicated that the inhibitors would also be active against arachidonate 5-lipoxygenase, an enzyme of leukotriene (LT) biosynthesis. This was verified by testing their inhibitory effects on 5-lipoxygenase prepared from RBL-1 cells. A diarylheptanoid with catechol group was the most active compound against 5-lipoxygenase, while yakuchinone A was the most active against PG synthetase.     

m-Diethynylbenzene macrocycles: syntheses and self-association behavior in solution

m-Diethynylbenzene macrocycles (DBMs), buta-1,3-diyne-bridged [4(n)]metacyclophanes, have been synthesized and their self-association behaviors in solution were investigated. Cyclic tetramers, hexamers, and octamers of DBMs having exo-annular octyl, hexadecyl, and 3,6,9-trioxadecyl ester groups were prepared by intermolecular oxidative coupling of dimer units or intramolecular cyclization of the corresponding open-chain oligomers. The aggregation properties were investigated by two methods, the (1)H NMR spectra and the vapor pressure osmometry (VPO). Although some discrepancies were observed between the association constants obtained from the two methods, the qualitative view was consistent with each other. The analysis of self-aggregation by VPO revealed unique aggregation behavior of DBMs in acetone and toluene, which was not elucidated by the NMR method. Namely, the association constants for infinite association are several times larger than the dimerization constant, suggesting that the aggregation is enhanced by the formation of dimers (a nucleation mechanism). In polar solvents, DBMs aggregate more strongly than in chloroform due to the solvophobic interactions between the macrocyclic framework and the solvents. Moreover, DBMs self-associate in aromatic solvents such as toluene and o-xylene more readily than in chloroform. In particular, the hexameric DBM having a large macrocyclic cavity exhibits extremely large association constants in aromatic solvents. By comparing the aggregation properties of DBMs with the corresponding acyclic oligomers, the effect of the macrocyclic structure on the aggregation propensity was clarified. Finally, it turned out that DBMs tend to aggregate more readily than the corresponding phenylacetylene macrocycles, acetylene-bridged [2(n)]metacyclophanes, owing to the withdrawal of the electron density from the aromatic rings by the butadiyne linkages which facilitates pi-pi stacking interactions.     

A GaCl3-catalyzed [4+1] cycloaddition of alpha,beta-unsaturated carbonyl compounds and isocyanides leading to unsaturated gamma-lactone derivatives

A GaCl3-catalyzed reaction of alpha,beta-unsaturated ketones with isocyanides leading to the formation of unsaturated lactone derivatives is described. This is the first example of the catalytic [4+1] cycloaddition of alpha,beta-unsaturated ketones and isocyanides. GaCl3 is an excellent catalyst due to its lower oxophilicity, which is desirable for all of the key steps, such as E/Z isomerization, cyclization, and deattachment from the products.     

Biooxidation of (+)-catechin and (-)-epicatechin into 3,4-dihydroxyflavan derivatives by the endophytic fungus Diaporthe sp. isolated from a tea plant

The microbial transformation of (+)-catechin (1) and (-)-epicatechin (2) by endophytic fungi isolated from a tea plant was investigated. It was found that the endophytic filamentous fungus Diaporthe sp. transformed them (1, 2) into the 3,4-cis-dihydroxyflavan derivatives, (+)-(2R,3S,4S)-3,4,5,7,3',4'-hexahydroxyflavan (3) and (-)-(2R,3R,4R)-3,4,5,7,3',4'-hexahydroxyflavan (7), respectively, whereas (-)-catechin (ent-1) and (+)-epicatechin (ent-2) with a 2S-phenyl group resisted the biooxidation.     

Reversible fixation and release of carbon dioxide with a binary system consisting of polyethylene glycol and polystyrene‐bearing cyclic amidine pendant group

In this study, we investigated the CO₂‐capture/release behavior of the polystyrene‐bearing cyclic amidine pendant groups, which was synthesized via free radical polymerization of HCl salt of the corresponding styrene monomer followed by neutralization. For comparison, we also prepared the polystyrene bearing N‐formyl‐1,3‐propanediamine pendant groups through the hydrolysis of the cyclic amidine group by treatment with an alkaline solution. First, we examined the CO₂‐capture/release behaviors of the amidine and amine monomers in aqueous solution in terms of conductivity. The conductivity of a wet DMSO solution of the amidine monomer increased upon CO₂ bubbling at 25 °C and reached a stationary value of about 11 mS/m, which indicated the formation of the bicarbonate salt. Conversely, the conductivity decreased to its original value upon N₂ bubbling at 50 °C, reflecting the complete release of the trapped CO₂ molecules. Both solutions showed the changes in the conductivity with quick responses, and no appreciable difference was observed between them. We then investigated the CO₂‐capture/release behaviors of the amidine and amine polymers, by taking advantage of the binary system with polyethylene glycol, and found that the binary system with the amidine polymer captured and released CO₂ more efficiently than that with the amine polymer. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2025–2031