Reaction of 4,5-diamino-1,6-dihydropyrimidin-6-ones with two equivalents of chalcones

The reaction of 4,5-diamino-1,6-dihydropyrimidin-6-ones 1 with two equivalents of the chalcones 2 leads in an acidic medium to the formation of the 2,3,6,7-tetrahydro-1H-pyrimido[4,5-b][1,4]diazepin-6-one derivatives 3a-d . The structure elucidation of the products is based on nmr measurements and an X-ray diffraction.     

Flexible synthetic route to 6-deoxy and 11-deoxyanthracyclinones

The regiospecific synthesis of 6-deoxydaunomycinone 3 and 1-hydroxy-4-demethoxy-11-deoxydaunomycinone (4) is reported: the route allows the preparation of 6-deoxy or 11-deoxyanthracyclinones through the γ or δ lactones 6 and 11.     

Linear total synthetic routes to beta-D-C-(1,6)-linked oligoglucoses and oligogalactoses up to pentaoses by iterative Wittig olefination assembly

Two complementary routes, A and B, have been followed for the stepwise iterative assembly of beta-D-(1,6)-glucopyranose and galactopyranose residues through methylene bridges. In route A the building block was constituted by 2,3,4-tri-O-benzyl-6-O-tert-butyldiphenylsilyl (O-TBDPS) beta-linked galactosylmethylenephosphorane, while in route B the building block was a beta-linked formyl C-glycopyranoside with a similar orthogonal protection of hydroxy groups. In route A each cycle consisted of the reaction of the phosphorane building block with a sugar residue bearing a formyl group at the C-5 carbon atom (coupling) and transformation of the O-TBDPS-protected primary alcohol into the formyl group (arming). Accordingly, route A is defined as the aldehyde route. On the other hand, each cycle in route B involved the coupling of the sugar aldehyde building block with a substrate bearing a phosphorus ylide at C-6 and introduction of the phosphonium group in the arming step as a precursor of the ylide functionality. Accordingly, route B is defined as the ylide route. The efficiency of route A proved to be seriously hampered by the 1,2-elimination of BnOH under the basic reaction conditions of the Wittig olefination, giving rise to the formation of substantial amounts of enopyranose. On the other hand, the ylide route B proved to be more efficient since very good yields (70-93%) of the isolated Wittig products were obtained throughout four consecutive cycles. Individual olefins and polyolefins obtained by routes A and B using gluco and galacto substrates were reduced and debenzylated in one pot by H(2)/Pd(OH)(2) to give the corresponding beta-D-C-(1,6)-linked oligosaccharides up to the pentaose stage. The latter compounds were fully characterized by high-field NMR spectroscopy (500 MHz).     

Stereoselective synthesis of alpha- and beta-L-C-fucosyl aldehydes and their utility in the assembly of C-fucosides of biological relevance

An efficient synthesis of O-benzylated derivatives of the title sugar aldehydes via thiazole addition to tri-O-benzyl-l-fuconolactone followed by highly stereoselective deoxygenation of the resulting thiazolylketose and thiazole to formyl transformation is described. Wittig olefination of these aldehydes with galactopyranose and glucopyranose 6-phosphoranes and reduction of the resulting alkenes afforded alpha- and beta-linked (1-->6)-L-C-fucosyl disaccharides, namely, beta-L-C-Fuc-(1-->6)-alpha-D-Gal, alpha-L-C-Fuc-(1-->6)-alpha-D-Gal, and alpha-L-C-Fuc-(1-->6)-alpha-d-Glc. The alpha-anomer of the above C-fucosyl aldehydes was transformed into a C-fucosylmethyl triphenylphosphonium iodide from which the corresponding C-fucosylmethylene phosphorane was generated upon treatment with BuLi. This phosphorane reacted with the Garner aldehyde (N-Boc D-serinal acetonide) and its one-carbon higher homologue to give alkenes whose reduction and unveiling of the glycinyl group from the oxazolidine ring afforded C-fucosyl alpha-amino acids, namely alpha-L-linked C-fucosyl serines and C-fucosyl asparagines. As a final test of the synthetic utility of the title aldehydes, the beta-anomer was employed as starting material in the stereoselective synthesis of both R- and S-epimer L-C-fucosyl phenylhydroxy acetates. One epimer was obtained by reaction of the sugar aldehyde with phenylmagnesium bromide, oxidation of the resulting alcohol to ketone, addition of 2-lithiothiazole to the latter, and transformation of the thiazole ring into the carboxyl group through an aldehyde intermediate. The other epimer was obtained by the same procedure and inverting the timing of phenyl and thiazolyl group addition. In both routes, the key step establishing the configuration of the quaternary carbon atom of the aliphatic chain was the highly stereoselective addition of the organometal to the ketone intermediate.     

Stoichiometric generation of magnesium homoenolate equivalents from acyltrimethylsilanes. Synthesis of 1,6-diketone derivatives

Treatment of various acyltrimethylsilanes with vinylmagnesium bromide has allowed a stoichiometric generation of the corresponding 3-(trimethyl-siloxy)allylmagnesiums, which, in the presence of copper(I) trimethylsilyl-acetylide, undergo conjugate addition to several enones to afford the corresponding 1,6-diketone derivatives in good yields.     

Para-acylcalix[6]arenes: their synthesis, per-O-functionalisation, solid-state structures and interfacial assembly properties

The para-acylcalix[6]arenes bearing butanoyl, hexanoyl and octanoyl chains have been synthesized by Friedel–Crafts acylation of the parent calixarene. Persubstitution at the phenolic face was achieved to yield the methoxy-diethoxy, ethoxycarbonylmethoxy, methoxycarboxylic acid and butoxysulphonate derivatives. In the case of the derivatives, 5,11,17,23,29,35-hexa-octanoyl-37,38,39,40,41,42-hexa-methoxy-diethoxy-calix[6]arene, 5,11,17,23,29,35-hexa-butanoyl-37,38,39,40,41,42-hexaethoxycarbonyl methoxy-calix[6]arene and 5,11,17,23,29,35-hexa-octanoyl-37,38,39,40,41,42-hexaethoxycarbonyl methoxy-calix[6]arene the solid state structures were determined and show inclusion of two ester groups in the cavity. While for the para-acylcalix[6]arenes no stable monolayers can be formed at the air–water interface, stable monolayers are formed with the methoxy-diethoxy, ethoxycarbonylmethoxy, methoxycarboxylato compounds which show apparent molecular areas in the range 150–200 Å² depending on the length of the acyl chains.     

First synthesis of 5-fluoro-(+)-MK7607, its 1-epimer and 6-deoxy derivative

(+)-MK7607 is a patented naturally occurring unsaturated pseudo-carbasugar possessing herbicidal activity. We present herein the first synthesis of the 5-fluorinated analogue (1S, 2S, 3R, 4R)-5-fluoro-6-(hydroxymethyl)cyclohex-5-ene-1,2,3,4-tetrol as well as that of two related compounds, namely its 1-epimer and its 6-deoxy derivative.     

Ruthenium(ii)-catalyzed regioselective 1,6-conjugate addition of umpolung aldehydes as carbanion equivalents

One of the most efficient and reliable approaches to construct C–C bonds involves the conjugate addition of carbon nucleophiles to electron-deficient ketones. Yet, 1,6-conjugate additions of extended conjugated systems largely remain underexplored due to difficulties in controlling the regioselectivity. Herein, we report umpolung aldehydes as carbanion equivalents for highly regioselective 1,6-conjugate addition reactions to unsaturated ketones, with preliminary studies of the enantioselective variant. The synergy of ruthenium(ii) catalyst and electron-rich, bidentate phosphine ligand is essential for the reactivity and selectivity under mild reaction conditions.

Highly regioselective 1,6-conjugate addition was developed using hydrazone as carbanion equivalent catalyzed by ruthenium under mild conditions.     

Per(6-guanidino-6-deoxy)cyclodextrins: synthesis, characterisation and binding behaviour toward selected small molecules and DNA

Per(6-guanidino-6-deoxy)-cyclodextrins , and are novel derivatives, resulting from homogeneous introduction of the guanidino group at the primary side of alpha-, beta- and gamma-cyclodextrins. The products were obtained from the corresponding amino derivatives, as direct guanidinylation of the known bromo-cyclodextrins provided mixtures. The new compounds were fully characterized by NMR spectroscopy and other analytical methods, and their interaction with guest molecules was studied. Strong complexation with 4-nitrophenyl phosphate () disodium salt was observed (K(binding) approximately 5 x 10(4) M(-1)), whereas the non-phosphorylated substrate nitrobenzene () formed a very weak complex. 2D ROESY spectra revealed cavity inclusion in both cases, however the orientation of was opposite to that of , such that the phosphate group is oriented toward the primary side facing the guanidine groups. The strong affinity of towards the phosphorylated guest suggested that interaction with DNA was possible. The new compounds were found to completely inhibit the migration of ultra pure calf thymus DNA during agarose gel electrophoresis, whereas no effects were observed with guanidine alone or with the plain cyclodextrins. Further, the condensation of DNA into nanoparticles in the presence of was demonstrated by atomic force microscopy, confirming strong electrostatic interaction between the biopolymer and the multicationic products . The strong guanidine-phosphate interactions between and DNA were therefore attributed to the clustering of the guanidine groups in the primary area of the cyclodextrin. Cavity effects could not be assessed.     

Poly-1,6-Diselenahexamethylene, 1,2-diselenane,and their effects on vinyl polymerizations

Poly-1,6-diselenahexamethylene has been prepared, and some of its properties and those of its depolymerization product, 1,2-diselenane, have been studied. Depolymerization probably occurs by a free-radical mechanism. The effects of these organoselenium compounds on the thermal polymerization of styrene, methyl methacrylate, vinyl acetate, and acrylonitrile at 60°C. in the presence and absence of 2,2′-azobisisobutyronitrile and on the direct photopolymerization of these vinyl monomers at 25°C. has been examined. Various reaction mechanisms are suggested to explain the experimental results.     

Synthesis of 1,6-Dideoxynojirimycin, 1,6-Dideoxy-D-allo-nojirimycin,and 1,6-Dideoxy-D-gulo-nojirimycin via Asymmetric Hetero-Diels-Alder Reactions

Asymmetric Diels-Alder reaction of sorbaldehyde O-methyloxime 1d with chiral chloronitroso derivative 2 of D -mannose, followed by osmylation of the primary cycloadduct, led to diol 6a with excellent enantioselectivity (ee > 99%; Scheme 1). Catalytic hydrogenolysis of 6a gave 1,6-dideoxy-D -allo-nojirimycin ( 7a ). Nucleophilic ring opening of cyclic sulfate 8 allowed a straightforward synthesis of 1,6-dideoxynojirimycin ( 11 ) and of 1,6-dideoxy-D -gulo-nojirimycin ( 12 ; Scheme 2).     

Solvent and guest isotope effects on complexation thermodynamics of alpha-, beta-, and 6-amino-6-deoxy-beta-cyclodextrins

The stability constant (K), standard free energy (DeltaG degrees ), enthalpy (DeltaH degrees ), and entropy changes (TDeltaS degrees ) for the complexation of native alpha- and beta-cyclodextrins (CDs) and 6-amino-6-deoxy-beta-CD with more than 30 neutral, positively, and negatively charged guests, including seven fully or partially deuterated guests, have been determined in phosphate buffer solutions (pH/pD 6.9) of hydrogen oxide (H(2)O) or deuterium oxide (D(2)O) at 298.15 K by titration microcalorimetry. Upon complexation with these native and modified CDs, both nondeuterated and deuterated guests examined consistently exhibited higher affinities (by 5-20%) in D(2)O than in H(2)O. The quantitative affinity enhancement in D(2)O versus H(2)O directly correlates with the size and strength of the hydration shell around the charged/hydrophilic group of the guest. For that reason, negatively/positively charged guests, possessing a relatively large and strong hydration shell, afford smaller K(H2O)/K(D2O) ratios than those for neutral guests with a smaller and weaker hydration shell. Deuterated guests showed lower affinities (by 5-15%) than the relevant nondeuterated guests in both H(2)O and D(2)O, which is most likely ascribed to the lower ability of the C-D bond to produce induced dipoles and thus the reduced intracavity van der Waals interactions. The excellent enthalpy-entropy correlation obtained can be taken as evidence for the very limited conformational changes upon transfer of CD complexes from H(2)O to D(2)O.     

Theoretical study of structures and properties of cyclobutadiene, cyclopentadiene and benzene and their nitrogen isoelectronic equivalents

B3LYP/aug-cc-pvDZ level of theory is applied to study the geometric structures, electronic topologies, heats of formation, hyperconjugations and steric repulsions of 27 kinds of compounds obtained by successive replacement of CH groups with nitrogen atoms in cyclobutadiene, cyclopentadiene and benzene. The results reveal that the total energy linearly decreases along with the replacement of CH groups by nitrogen atoms for the three systems. To estimate the potential of high nitrogen content high energy materials (HNC–HEMs), heats of formation are calculated by G3 method. With the increase of the number of nitrogen atoms in ring, heats of formation increase substantially. The four-membered ring system is found to have the greatest heat of formations, followed by the six-membered ring system, and then by the five-membered ring system. Especially, hexazine and tetraazacyclobutadiene have great heats of formation relative to the other compounds, which implies that they should be applicable as HNC–HEMs. In addition, our studies indicate that the relationship between the total energy or heats of formation of isomers and the position of nitrogen atoms is (ortho) meta < (ortho) para < ortho. NBO analysis shows that it is hyperconjugation, not steric repulsion that plays a key role in the relative stability of isomers.     

Monodisperse nanocrystals: general synthesis, assembly, and their applications

This article summarizes the recent advances in the synthesis, assembly and applications of monodisperse nanocrystals, which may be suggestive for the designed synthesis and assemblies of target nanocrystals according to practical requirements.     

辛醛VC缩醛的合成及其在茶籽油中的抗氧化性能

缩醛类化合物由于保持了原来醛类化合物所具有的珍贵香气,且留香持久,香气类型多,在调香中有很高的使用价值[1,2]。辛醛有很强的水果香味,在极稀时有令人愉快的甜橙香气,是我国GB2760-86规定暂时允许使用的食用香料,主要用于饮料、冰淇淋、糖果、面包中以及柑橘类香料的调合[3]     

Rapid assembly of the procyanidin A skeleton

Arylpropynals and two equivalents of phloroglucinol react to produce pentacyclic ketals. In addition, 4-methoxydibromocinnamaldehyde also reacted to form procyanidin A-skeleton.     

The haplotype assembly model with genotype information and iterative local-exhaustive search algorithm

The minimum error correction (MEC) model for haplotype reconstruction is efficient only when the error rate in SNP fragments is low. In order to improve reconstruction rate, additional genotype information is added into MEC model as an extension to MEC model. In this paper, we first establish a new mathematical model for haplotype assembly problem with genotype information. Several properties of the mathematical model are proved. Then an iterative local-exhaustive search algorithm is proposed based on the model and its properties. The main idea is to find the optimal pair among 2(l-1) (l denotes the number of heterozygous sites of a genotype) haplotype pairs by performing local exhaustive search for the promising haplotype pair step by step. By experiments and comparison, extensive numerical results on real data and simulated data indicate that our algorithm outperforms the other algorithms in terms of efficiency and robustness.     

The preparation of 1,2,4-triazines from α,β-diketo-ester equivalents and their application in pyridine synthesis

The α-Chloro-α-acetoxy-β-keto-esters were prepared from β-keto-esters in good overall yields. These compounds reacted as α,β-diketo-ester equivalents with amidrazones yielding triazines, generally in good yields, or with an amidrazone and 2,5-norbornadiene in a one-pot aza Diels-Alder reaction to give the corresponding pyridines.     

Surface and thermodynamic properties of octyl, dodecyl, and cetyl sulfoacetates

Summary Three anionic surfactants (Na-octysulfoacetate (A ₈), Na-dodecylsulfoacetate (A ₁₂), and Na-cetylsulfoacetate (A ₁₆) were prepared from alkyl bromoacetate. Several studies were carried out with aqueous surfactant solutions including surface tension, and electrical conductivity measurements. Surface properties, in particular, critical micelle concentration (CMC), effectiveness ( _CMC ), efficiency (P _c20), maximum surface excess (_max), and minimum surface area (A _min) were investigated at different concentrations at 20, 35 and 50°C, respectively. Free energies, enthalpies, entropies of micellization, and adsorption of the surfactants in the aqueous solution were studied.

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Thermodynamik und Oberflächeneigenschaften von Octyl-, Dodecyl- und Cetylsulfoacetaten

Zusammenfassung Drei anionische Tenside (Na-Octylsulfoacetat (A ₈), Na-Dodecylsulfoacetat (A ₁₂) und Na-Cetylsulfoacetat (A ₁₆)) wurden aus Bromessigsäurealkylestern hergestellt. An wäßrigen Lösungen der Tenside wurden deren Oberflächenspannung und elektrische Leitfähigkeit gemessen. Oberflächeneigenschaften, insbesondere kritische Micellenkonzentration (MCC), Effektivität ( _CMC ), Effizienz (P _c20) maximaler Oberflächenüberschuß (_max) und minimale Oberfläche (A _min) wurden bei verschiedenen Konzentrationen und bei Temperaturen von 20, 35 und 50°C untersucht. Die freien Energien, Enthalpien, Entropien und die Adsorption der Tenside in wäßriger Lösung wurden bestimmt.