Synthesis of Indoles from N-Substituted Anilines and Triethanolamine by a Homogeneous Ruthenium Catalyst

N-substituted anilines react with triethanolamine in the presence of a catalytic amount of a homogeneous ruthenium catalyst to give the corresponding 1-substituted indoles in good yields.     

Synthesis of All Stereoisomers of Monomeric Spectomycin A1/A2 and Evaluation of Their Protein SUMOylation-Inhibitory Activity

A synthetic methodology to access all possible stereoisomers of spectomycin A1 (SMA1) and A2 (SMA2) has been established through late-stage diversification. The key reaction for the construction of all four diastereomers is an intramolecular cyclization based on the umpolung of π-allyl palladium species with bis(pinacolato)diborane (B₂(pin)₂). Silyl group assisted direct benzylic oxidation of each isomer enabled construction of the fragile β-hydroxytetralone skeleton to provide the SMAs. The relative and absolute stereochemistry of SMA2 was also determined, and the absolute stereochemistry of SMA1 was extrapolated based on the optical rotation of SMA2. The axial chirality of SMAs is discussed based on circular dichroism spectra and DFT calculations, and it is concluded that the M isomer is predominant in solution. Biochemical assessment of all isomers in vitro revealed that the C9 hydroxyl group and dimeric structure were both important for protein SUMOylation-inhibitory activity.     

Power of isotopic fine structure for unambiguous determination of metabolite elemental compositions: In silico evaluation and metabolomic application

In mass spectrometry (MS)-based metabolomics studies, reference-free identification of metabolites is still a challenging issue. Previously, we demonstrated that the elemental composition (EC) of metabolites could be unambiguously determined using isotopic fine structure, observed by ultrahigh resolution MS, which provided the relative isotopic abundance (RIA) of ¹³C, ¹⁵N, ¹⁸O, and ³⁴S. Herein, we evaluated the efficacy of the RIA for determining ECs based on the MS peaks of 20,258 known metabolites. The metabolites were simulated with a ≤25% error in the isotopic peak area to investigate how the error size effect affected the rate of unambiguous determination of the ECs. The simulation indicated that, in combination with reported constraint rules, the RIA led to unambiguous determination of the ECs for more than 90% of the tested metabolites. It was noteworthy that, in positive ion mode, the process could distinguish alkali metal-adduct ions ([M + Na]⁺ and [M + K]⁺). However, a significant degradation of the EC determination performance was observed when the method was applied to real metabolomic data (mouse liver extracts analyzed by infusion ESI), because of the influence of noise and bias on the RIA. To achieve ideal performance, as indicated in the simulation, we developed an additional method to compensate for bias on the measured ion intensities. The method improved the performance of the calculation, permitting determination of ECs for 72% of the observed peaks. The proposed method is considered a useful starting point for high-throughput identification of metabolites in metabolomic research.     

Reversible and Stepwise Single-Crystal-to-Single-Crystal Transformation of a Platinum(II) Complex with Vapochromic Luminescence

The vapochromic single-crystal-to-single-crystal (SCSC) transformation of a highly luminescent Pt^II complex bearing an N-heterocyclic carbene [Pt(CN)₂(tBu-impy)] (tBu-impyH⁺=1-tert-butyl-3-(2-pyridyl)-1H-imidazolium) is reported. The trihydrate form of the complex, which exhibits blue ³MMLCT emission owing to weak Pt⋅⋅⋅Pt interactions, changed its luminescence color from blue to yellowish-green upon the desorption of water molecules while keeping the high emission quantum yield of more than 0.45. Variable-temperature and continuous in-situ tracking of single-crystal X-ray diffraction measurements revealed that the SCSC transformation proceeds reversibly by the release and reabsorption of water molecules, thereby changing the stacked structure slightly. As a result, the dynamics of vapor-induced SCSC transformation were elucidated: that the anhydrous form returned to the original trihydrate form in a two-step process under a water vapor atmosphere. In addition, the Pt^II complex exhibited a similar SCSC response accompanied by a luminescence color change in the presence of methanol vapor, while being inactive toward ethanol vapor.     

Alkane Shape- and Size-Recognized Selective Vapor Sorption in “Channel-Like” Crystals Based on Thiacalixarene Assemblies

Alkanes composed of C−C and C−H show a low electric polarization, and therefore, there is only very weak interaction between alkanes and adsorbents. Thus, it is difficult to separate a specific alkane from a mixture of alkanes by adsorption. Here, two activated “channel-like” crystals generated from brominated thiacalix[4]arene propyl ethers, which adopt 1,3-alternate and partial cone conformations, recognize specific alkane vapors depending on alkane-shape and -size, sorting in three-type alkane guests such as linear, branched, and cyclic alkanes. Two activated crystals, which are prepared by removal of solvent upon heating under reduced pressure, incorporate branched and/or cyclic alkane vapors by a unique “gate-opening” mechanism via a crystal transformation in the process. Linear alkane vapors do not trigger gate opening and are not taken up by the activated crystals. The shape and size molecular-recognition properties of the activated crystals promises considerable usefulness for the separation of linear, branched, and cyclic alkanes.     

Highly Selective Asymmetric Intramolecular Selenocyclisation

Asymmetric intramolecular selenocyclisation of alkenoic acids, alkenols and alkenyl urethanes using chiral ferrocenylselenenyl cations proceeds smoothly to give the corresponding lactones, cyclic ethers and N-heterocyclic compounds, respectively, in moderate yields with very high diastereoselectivities.     

Chiral Bis(oxazoline)-copper Catalyzed Enantioselective Imidation of Sulfides

Prochiral sulfides reacted with Phl=NTs in the presence of a catalytic amount of Cu(I) salt together with a chiral 4,4′-disubstituted bis(oxazoline) ligand to afford the corresponding chiral sulfimides.     

Binding of acetylcholine and quaternary ammonium compounds to a C3-symmetric bowl-shaped tripeptide of 2-(3-aminophenoxy)propanoic acids acting as a ditopic receptor

The new tripeptide reported here is composed of (R)-2-(3-aminophenoxy)propionic acid and is a bowl-shaped receptor that simultaneously binds both cations and anions of acetylcholine chloride and benzyltrimethylammonium compounds. An intriguing conformational change of the host was observed in the complexation of the ionic pair, where anion-induced flipping of the amide group on the macrocycle occurred.