Asymmetric Total Syntheses,Stereostructures, and Cytotoxicities of Marine Bromotriterpenoids Aplysiol B (Laurenmariannol) and Saiyacenol A

There are marine cytotoxic bromotriterpenoids, named the thyrsiferol family that are structurally characterized by some tetrahydropyran (THP) and tetrahydrofuran (THF) rings. The thyrsiferol family belongs to natural products that are often difficult to determine their stereostructures even by the current, highly advanced spectroscopic methods, especially in acyclic systems including stereogenic tetrasubstituted carbon centers. In such cases, it is effective to predict and synthesize the possible stereostructures. Herein, to elucidate ambiguous stereostructures and unassigned absolute configurations of aplysiol B, laurenmariannol, and saiyacenol A, members of the thyrsiferol family, we carried out their asymmetric chemical syntheses featuring 6-exo and 5-exo oxacyclizations of epoxy alcohol precursors and 6-endo bromoetherification of a bishomoallylic alcohol. In this paper, we report total assignments of their stereostructures through their asymmetric chemical syntheses and also their preliminary cytotoxic activities against some tumor cells. These results could not have been achieved without depending on asymmetric total synthesis.     

Sonochemical conversion of CO2 into hydrocarbons: The Sabatier reaction at ambient conditions

In this study, we investigated an alternative method for the chemical CO₂ reduction reaction in which power ultrasound (488 kHz ultrasonic plate transducer) was applied to CO₂-saturated (up to 3%) pure water, NaCl and synthetic seawater solutions. Under ultrasonic conditions, the converted CO₂ products were found to be mainly CH₄, C₂H₄ and C₂H₆ including large amount of CO which was subsequently converted into CH₄. We have found that introducing molecular H₂ plays a crucial role in the CO₂ conversion process and that increasing hydrogen concentration increased the yields of hydrocarbons. However, it was observed that at higher hydrogen concentrations, the overall conversion decreased since hydrogen, a diatomic gas, is known to decrease cavitational activity in liquids. It was also found that 1.0 M NaCl solutions saturated with 2% CO₂ + 98% H₂ led to maximum hydrocarbon yields (close to 5%) and increasing the salt concentrations further decreased the yield of hydrocarbons due to the combined physical and chemical effects of ultrasound. It was shown that CO₂ present in a synthetic industrial flue gas (86.74% N₂, 13% CO₂, 0.2% O₂ and 600 ppm of CO) could be converted into hydrocarbons through this method by diluting the flue gas with hydrogen. Moreover, it was observed that in addition to pure water, synthetic seawater can also be used as an ultrasonicating media for the sonochemical process where the presence of NaCl improves the yields of hydrocarbons by ca. 40%. We have also shown that by using low frequency high-power ultrasound in the absence of catalysts, it is possible to carry out the conversion process at ambient conditions i.e., at room temperature and pressure. We are postulating that each cavitation bubble formed during ultrasonication act as a “micro-reactor” where the so-called Sabatier reaction -$C{O}_2+4H_2\stackrel{\mathit{Ultrasonication}}{\to }C{H}_4+2H_{2}O$ - takes place upon collapse of the bubble. We are naming this novel approach as the “Islam-Pollet-Hihn process”.     

Mechanism of BPh3-Catalyzed N-Methylation of Amines with CO2 and Phenylsilane: Cooperative Activation of Hydrosilane

BPh₃ catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO₂ and PhSiH₃; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C₆F₅)₃ shows little or no activity. ¹¹B NMR spectra suggested the generation of [HBPh₃]⁻. The detailed mechanism of the BPh₃-catalyzed N-methylation of N-methylaniline ( 1 ) with CO₂ and PhSiH₃ was studied by using DFT calculations. BPh₃ promotes the conversion of two substrates (N-methylaniline and CO₂) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N⁺CO₂⁻⋅⋅⋅BPh₃]. The carbamate and BPh₃ act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH₃ to generate [HBPh₃]⁻, which is used to produce key CO₂-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh₃]⁻ species.     

Mechanistic Aspects of a Highly Active Dinuclear Zinc Catalyst for the Co‐polymerization of Epoxides and CO2

The dinuclear zinc complex reported by us is to date the most active zinc catalyst for the co‐polymerization of cyclohexene oxide (CHO) and carbon dioxide. However, co‐polymerization experiments with propylene oxide (PO) and CO₂ revealed surprisingly low conversions. Within this work, we focused on clarification of this behavior through experimental results and quantum chemical studies. The combination of both results indicated the formation of an energetically highly stable intermediate in the presence of propylene oxide and carbon dioxide. A similar species in the case of cyclohexene oxide/CO₂ co‐polymerization was not stable enough to deactivate the catalyst due to steric repulsion.     

Structure determination of KScS2, RbScS2 and KLnS2 (Ln = Nd,Sm, Tb,Dy, Ho,Er, Tm and Yb) and crystal–chemical discussion

The title structures of KScS₂ (potassium scandium sulfide), RbScS₂ (rubidium scandium sulfide) and KLnS₂ [Ln = Nd (potassium neodymium sufide), Sm (potassium samarium sulfide), Tb (potassium terbium sulfide), Dy (potassium dysprosium sulfide), Ho (potassium holmium sulfide), Er (potassium erbium sulfide), Tm (potassium thulium sulfide) and Yb (potassium ytterbium sulfide)] are either newly determined (KScS₂, RbScS₂ and KTbS₂) or redetermined. All of them belong to the α‐NaFeO₂ structure type in agreement with the ratio of the ionic radii r³⁺/r⁺. KScS₂, the member of this structural family with the smallest trivalent cation, is an extreme representative of these structures with rare earth trivalent cations. The title structures are compared with isostructural alkali rare earth sulfides in plots showing the dependence of several relevant parameters on the trivalent cation crystal radius; the parameters thus compared are c, a and c/a, the thicknesses of the S—S layers which contain the respective constituent cations, the sulfur fractional coordinates z(S²⁻) and the bond‐valence sums.     

Tuning the Basicity of Cyano‐Containing Ionic Liquids to Improve SO2 Capture through Cyano–Sulfur Interactions

A new approach has been developed to improve SO₂ sorption by cyano‐containing ionic liquids (ILs) through tuning the basicity of ILs and cyano–sulfur interaction. Several kinds of cyano‐containing ILs with different basicity were designed, prepared, and used for SO₂ capture. The interaction between these cyano‐containing ILs and SO₂ was investigated by FTIR and NMR methods. Spectroscopic investigations and quantum chemical calculations showed that dramatic effects on SO₂ capacity originate from the basicity of the ILs and enhanced cyano–sulfur interaction. Furthermore, the captured SO₂ was easy to release by heating or bubbling N₂ through the ILs. This efficient and reversible process, achieved by tuning the basicity of ILs, is an excellent alternative to current technologies for SO₂ capture.     

A simple,rapid and sensitive method based on modified multiwalled carbon nanotube for preconcentration and determination of lead ions in aqueous media in natural pHs

In this study, multiwalled carbon nanotube (MWCNT) was modified by the pyridine group using a silane agent and characterized by infrared spectroscopy (IR), thermal analysis (TG/DTA), and elemental analysis (CHN) and scanning electron microscopy (SEM). The application of this sorbent was investigated in determination of lead ions in aqueous samples, using flame atomic absorption spectrometry (FAAS). Through this study, different parameters such as pH and sample flow rate on adsorption process and eluent concentration, volume and flow rate were optimized. The limit of detection (LOD), the relative standard deviation and the recovery of the method were 2 ng mL^?1, 1.3% and 99.7%, respectively. Two standard reference materials (NIST 1571 and NIST 1572) were used to verify accuracy of this method. Finally, the sorbent was successfully applied for extraction and determination of low levels of Pb(II) ions in aqueous samples.     

Thermally induced solid-state transformation of cimetidine. A multi-spectroscopic/chemometrics determination of the kinetics of the process and structural elucidation of one of the products as a stable N3-enamino tautomer

Exposure of cimetidine (CIM) to dry heat (160–180 °C) afforded, upon cooling, a glassy solid containing new and hitherto unknown products. The kinetics of this process was studied by a second order chemometrics-assisted multi-spectroscopic approach. Proton and carbon-13 nuclear magnetic resonance (NMR), as well as ultraviolet and infrared spectroscopic data were jointly used, whereas multivariate curve resolution with alternating least squares (MCR-ALS) was employed as the chemometrics method to extract process information. It was established that drug degradation follows a first order kinetics.