Strategies for Accessing cis-1-Amino-2-Indanol.

cis-1-amino-2-indanol is an important building block in many areas of chemistry. Indeed, this molecule is currently used as skeleton in many ligands (BOX, PyBOX…), catalysts and chiral auxiliaries. Moreover, it has been incorporated in numerous bioactive structures. The major issues during its synthesis are the control of cis-selectivity, for which various strategies have been devised, and the enantioselectivity of the reaction. This review highlights the various methodologies implemented over the last few decades to access cis-1-amino-2-indanol in racemic and enantioselective manners. In addition, the various substitution patterns on the aromatic ring and their preparations are listed.

Compact Combustion Mechanisms of Typical n-Alkanes Developed by the Minimized Reaction Network Method.

The existing combustion kinetic modeling method which aims at developing phenomenological combustion mechanisms characterized by multiple reactions confronts several challenges, including the conflicts between computing resources and mechanism scales during numerical simulation, etc. In order to address these issues, the minimized reaction network method for complex combustion system modeling based on the principle of simultaneous chemical equilibrium is proposed, which is aimed to develop combustion mechanisms with minimal reaction steps under a limited number of species. The concept of mechanism resolution is proposed in this method, and the reaction network with minimal reaction steps under a given mechanism resolution is constructed so that the scale of mechanisms is compressed greatly. Meanwhile, distinguishing from other mechanisms, the reversible form of elementary reactions is adopted and the classical two-parameter (A, Ea) Arrhenius equation fits the rate constants. Typical n-alkanes including n-butane, n-heptane, n-octane, n-decane, n-dodecane and n-hexadecane were taken as examples to indicate the development process of mechanisms and systematic kinetic validations were carried out. Results show that this method leads to very compact mechanisms with satisfactory accuracy, and it eliminates the process of mechanism reduction and is beneficial for mechanism optimization. This method and the derived kinetic mechanisms are hoped to contribute to combustion engineering applications.

The preparation of optically active epineoclausenamide and enantiomeric separation of its racemate.

We synthesized the optically active epineoclausenamide by utilizing chiral reagents, such as R-α-methylbenzylamine and S-α-methylbenzylamine, for the resolution of the intermediate (trans-3-phenyl-oxiranecarboxylic acid 12), followed by amide exchange, cyclization, and reduction, unlike previously reported methods. The Meerwein-Ponndorf-Verley reduction was used to asymmetrically reduce neoclausenamidone. A plausible reduction mechanism of this method was elucidated. Thereafter, high-performance liquid chromatography (HPLC) was investigated for the resolution of the epineoclausenamide enantiomers. HPLC was also used to determine the optical purity of these isomers. Two chiral stationary phases (CSPs) for separating the enantiomers were compared. Different mobile phase compositions were tested at 298.15 K. The results showed that the best separation was obtained when the mobile phase was composed of n-hexane and isopropanol (IPA) (75/25, v/v), the racemate was separated on a Chiralcel OJ-H column, and the flow rate was 1.0 mL/min at a wavelength of 210 nm and a temperature of 25°C. The enantiomeric ratio (e.r.) values of both the synthetic (-)-epineoclausenamide and (+)-epineoclausenamide were 1.3(+):98.7(-) and 99.3(+):0.7(-), respectively. In this study, a new synthetic route was designed with a yield of 12.3-14.1%, and a quick (8 min) effective separation method was obtained. This provides basis for pharmacological research and quality control of clausenamide analogues.

Lactones in the Synthesis of Prostaglandins and Prostaglandin Analogs.

In the total stereo-controlled synthesis of natural prostaglandins (PGs) and their structural analogs, a vast class of compounds and drugs, known as the lactones, are encountered in a few key steps to build the final molecule, as: δ-lactones, γ-lactones, and 1,9-, 1,11-, and 1,15-macrolactones. After the synthesis of 1,9-PGF2α and 1,15-PGF2α lactones, many 1,15-lactones of E2, E3, F2, F3, A2, and A3 were found in the marine mollusc Tethys fimbria and the quest for understanding their biological role stimulated the research on their synthesis. Then 1,9-, 1,11-, and 1,15-PG lactones of the drugs were synthesized as an alternative to the corresponding esters, and the first part of the paper describes the methods used for their synthesis. The efficient Corey procedure for the synthesis of prostaglandins uses the key δ-lactone and γ-lactone intermediates with three or four stereocenters on the cyclopentane fragment to link the PG side chains. The paper describes the most used procedures for the synthesis of the milestone δ-Corey-lactones and γ-Corey-lactones, their improvements, and some new promising methods, such as interesting, new stereo-controlled and catalyzed enantioselective reactions, and methods based on the chemical/enzymatic resolution of the compounds in different steps of the sequences. The many uses of δ-lactones not only for the synthesis of γ-lactones, but also for obtaining 9ß-halogen-PGs and halogen-substituted cyclopentane intermediates, as synthons for new 9ß-PG analogs and future applications, are also discussed.

On the effect of using collision/reaction cell (CRC) technology in single-particle ICP-mass spectrometry (SP-ICP-MS).

In this work, the effects of using collision/reaction cell (CRC) technology in quadrupole-based ICP-MS (ICP-QMS) instrumentation operated in single-particle (SP) mode have been assessed. The influence of (i) various CRC gases, (ii) gas flow rates, (iii) nanoparticle (NP) sizes and (iv) NP types was evaluated using Ag, Au and Pt NPs with both a traditional ICP-QMS instrument and a tandem ICP-mass spectrometer. It has been shown that using CRC technology brings about a significant increase in the NP signal peak width (from 0.5 up to 6 ms). This effect is more prominent for a heavier gas (e.g., NH3) than for a lighter one (e.g., H2 or He). At a higher gas flow rate and/or for larger particle sizes >100 nm), the NP signal duration was prolonged to a larger extent. This effect of using CRC technology has been further demonstrated by characterizing custom-made 50 and 200 nm Fe3O4 NPs (originally strongly affected by the occurrence of spectral overlap) using different CRC approaches (H2 on-mass and NH3 mass-shift). The use of NH3 (monitoring of Fe as the Fe(NH3)2+ reaction product ion at m/z = 90 amu) induces a significant peak broadening compared to that observed when using H2 (6.10 ±â€¯1.60 vs. 0.94 ±â€¯0.49 ms). This extension of transit time can most likely be attributed to the collisions/interactions of the ion cloud generated by a single NP event with the CRC gas and it even precludes 50 nm Fe3O4 NPs to be detected when using the NH3 mass-shift approach. Based on these results, the influence of a longer peak width on the accuracy of SP-ICP-MS measurement data (NP size, particle number density and mass concentration) must be taken into account when using CRC technology as a means to overcome spectral overlap. To mitigate the potential detrimental effect of using CRC technology in the characterization of NPs via SP-ICP-MS(/MS), the use of light gases and low gas flow rates is recommended.