Silver(I)‐Catalyzed Enantioselective [3+2]‐Cycloaddition Reaction of α‐Silylimines: A Facile Route to Quaternary‐Carbon‐Rich Scaffolds

A silver‐catalyzed highly enantioselective 1,3‐dipolar cycloaddition reaction of α‐silylimines with pyrone‐based trisubstituted olefins was developed affording bi‐ and tricyclic α‐quaternary‐carbon‐rich pyrano‐pyrrolidines in excellent yields. The tricyclic benzopyrone adducts thus obtained were efficiently transformed into highly complex tetracyclic scaffolds supporting four consecutive stereogenic centers with three quaternary carbons.     

Metal-free,PTSA catalyzed facile synthesis of β-ketoacetal from β-chlorocinnamaldehyde

A toluene solution of β-chlorocinnamaldehyde and dihydroxy alcohols in the catalytic presence of para-toluenesulphonic acid (PTSA) yield the β-ketoacetal in good to outstanding amount. The catalyst (PTSA), first selectively protect the aldehydic group to form the β-chloroacetal and the subsequent dechlorination by H₂O result the β-ketoacetal. Significant transformation was achieved with electron donating substituent attached at the para-position of cinnamaldehyde. The selective formation of β-keto-1,3-acetal was also obtained with a mixture of 1, 2- and 1, 3- diol. The present reaction consists of a metal-free, economical, robustly feasible, sizeable functional group tolerance and high yield properties. Moreover, the use of different dihydroxy alcohols made this process more benign and valuable towards the metal-free development of ketones. First, of its kind, a rare and unusual multitasking nature of PTSA is observed.     

Selective and efficient oxidation of sulfides to sulfoxides using ammonium cerium (IV) nitrate in the presence of a catalytic amount of KBr or NaBr

A wide range of aliphatic or aromatic sulfides are selectively oxidized to the corresponding sulfoxides using ammonium cerium (IV) nitrate (CAN) and a catalytic amount of KBr or NaBr in the presence of wet SiO₂ in CH₂Cl₂ under heterogeneous conditions in moderate to high yields.     

Selective and efficient oxidation of sulfides to sulfoxides using ammonium cerium (IV) nitrate in the presence of a catalytic amount of KBr or NaBr

A wide range of aliphatic or aromatic sulfides are selectively oxidized to the corresponding sulfoxides using ammonium cerium (IV) nitrate (CAN) and a catalytic amount of KBr or NaBr in the presence of wet SiO₂ in CH₂Cl₂ under heterogeneous conditions in moderate to high yields. Correspondence: Mohammad Ali Zolfigol, Faculty of Chemistry, Bu-Ali Sina University, P.O. Box 6517838683, Hamadan, Iran; Kamal Amani, Department of Chemistry, Faculty of Science, University of Kurdistan, P.O. Box 6617715175, Sanandaj, Iran.     

A new thermal study of the reaction of 6‐azidopyridones with different amines and hydrazines

Reacting of 6‐azidopyridone derivatives 1 with o‐phenylenediamine ( 2a ) in chloroform at room temperature afforded the new azidopyridones 3 . However, its fusion with 2a,b at 100–110°C gave the interesting pyrido[2,3‐b][1,5]diazepines 4a,b . Alternatively, compound 4a could also be obtained by heating azidopyridones 3 at 100–110°C. When compound 1 was allowed to react with hydrazines 7a‐d at room temperature it gave the corresponding azido compounds 8a‐d . Fusion of 1 with phenylhydrazine ( 7d ) at 140–160°C afforded the new aminopyridones 10 . The 6‐azidopyridones 1 could also be converted to the corresponding 6‐alkylaminopyridones 15a‐d by reaction with an excess of alkylamines at room temperature.     

Fused polyaza‐heterocycles and 1,3,4‐thiadiazoles via a tricyano synthon

Treatment of 2‐cyano‐3‐phenyl‐2‐pentenedinitrile with some heterocyclic diazonium salts afforded the corresponding heterocyclic hydrazones. Some of the latter hydrazones were converted into fused polyaza‐heterocycles upon boiling in pyridine. Reaction of 2‐cyano‐3‐phenyl‐2‐pentenedinitrile with phenylisothiocyanate gave a tricyano‐thiole derivative which on treatment with hydrazonoyl chlorides and 1‐(benzothiazol‐2‐yl)‐2‐bromoethanone furnished 1,3,4‐thiadiazole and thiazole derivatives, respectively.     

Evaluation of a new matrix-free laser desorption/ionization method through statistic studies: comparison of the DIAMS (desorption/ionization on self-assembled monolayer surface) method with the MALDI and TGFA-LDI techniques

This work demonstrates that the desorption/ionization on self-assembled monolayer surface (DIAMS) mass spectrometry, a recent matrix-free laser desorption/ionization (LDI) method based on an organic target plate, is as statistically repeatable and reproducible as matrix assisted laser desorption ionization (MALDI) and thin gold film-assisted laser desorption/ionization (TGFA-LDI) mass spectrometries. On lipophilic DIAMS of target plates with a mixture of glycerides, repeatability/reproducibility has been estimated at 15 and 30% and the relative detection limit has been evaluated at 0.3 and 3 pmol, with and without NaI respectively. Salicylic acid and its d(6)-isomer analysis confirm the applicability of the DIAMS method in the detection of compounds of low molecular weight.     

Molecular selectivity and immiscibility during the crystallization of mixtures of a set of homologous self-assembling molecules

Utilizing self-assembly to create supramolecular structures is an active area at this time. Hybrid materials created by blending or doping, e.g., organic/inorganic or donor/acceptor complexes are of great interest in the design of novel materials systems. The effect of mixing of any two self-assembling molecules to modify the properties and to understand if the process of blending changes the nature of the self-assembly would be of interest. We discuss here the effect of blending of two (hydrogen bond mediated) self-assembling homologous molecules on the structure and morphology. Materials that are candidate vehicles for phase-change inkjet technology, biscarbamates with alkyl side chains, are chosen for this study. Thermal analysis and IR spectra indicate that, when two biscarbamates differing only in the length of the alkyl chain are blended, the two components are immiscible, although they are chemically similar. There is no intercalation of the alkyl chains and cocrystallization. They are thus an example of a self-sorting system. The extent of hydrogen bonding and the packing of the alkyl chains are not affected. However, each serve as a nucleating agent and reduce the size of the spherulites and crystallinity. The spherulitic growth rate decreases upon blending. Partial melting experiments show that the spherulites of each component do not form independently, but are intermixed, implying that one acts as the nucleating sites for the other. Thus, although these are self-sorting, the components in the mixture affect the morphology of each other upon crystallization. The behavior of this small molecule mixture is compared with those of hydrogen-bonded polymer blends. Studies of this nature on blends of self-assembling molecules are expected to be important in materials design for optimizing properties.     

Modulating the framework negative charge density in the system [BDT-TTP*+]/[Re6S5Cl9(1-)]/[Re6(S/Se)6Cl8(2-)]/[Re6S7Cl7(3-)]: templating by isosteric cluster anions of identical symmetry and shape, variations of incommensurate band filling, and electronic structure in 2D metals

A series of 2D metals, beta-(BDT-TTP)6[Re6Se6Cl8] x (CHCl2-CHCl2)2, 2; beta-(ST-TTP)6[Re6S6Cl8] x (CH2Cl-CHCl2)2, 3; beta-(BDT-TTP)7[Re6S6Cl8]0.5[Re6S7Cl7]0.5 x (CH2Cl2), 4; beta-(BDT-TTP)7[Re6Se6Cl8]0.5[Re6S7Cl7]0.5 x (CH2Cl2), 5; beta-(BDT-TTP)8[Re6S7Cl7] x (CH2Cl2)4, 6 (BDT-TTP and ST-TTP are 2,5-bis(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene and 2-(1,3-diselenol-2-ylidene)-5(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene, respectively) is reported to have one single beta-slab layered topology despite successive increases of the cluster anion negative charge. The charge density within the templating composite inorganic-neutral molecule slab is shown to remain above a threshold of ca. one negative charge per square nanometer, that is, for cluster anions with two negative charges and higher. Conversely, discrete stacks are shown to be stabilized instead in the semiconducting salts (BDT-TTP)2[Re6S5Cl9], 1 where the cluster anion bears one negative charge only. The electronic structure of salts 2-6 is shown to be very stable and kept almost intact across the series. The templating strategy is shown to fulfill its anticipated potential for deliberate installment of incommensurate band fillings in molecular metals. The deliberate admixture of the 6:1 and 8:1 structures yields novel phases with a 7:1 stoichiometry with the anticipated crystal and electronic structures. The action at the organic-inorganic interface triggered by changing the anion charge yet keeping its shape and volume identical, which ultimately governs the shape of the unit cell, is of paramount importance in defining the Fermi surface of these metallic salts. The present BDT-TTP salts thus provide a series of materials with strongly related but subtly different Fermi surfaces worthy of many physical studies. Shubnikov-de Haas measurements are expected to be particularly interesting since they are especially sensitive to the details of the Fermi surface.