Photoinduced tandem three-component coupling of propanedinitrile, 2,5-dimethylhexa-2,4-diene, and cyanoarenes

A tandem three-component coupling photoreaction proceeds upon photoirradiation of MeCN/H2O solutions containing propanedinitrile (1, malononitrile), 2,5-dimethylhexa-2,4-diene (2), and polycyanoarenes in the presence of phenanthrene and carbonate, leading to selective alpha-monoalkylation of 1. The reaction proceeds via photo-NOCAS (Nucleophile-Olefin Combination, Aromatic Substitution) type mechanism: nucleophilic attack of the anion of 1 to photogenerated 2(*+) is followed by ipso-substitution on the radical anion of the polycyanoarene. It advances under mild, safe, and environmentally friendly conditions such as proceeding at ambient temperature without metals and halogens, and in the presence of weak base. The reaction also represents a novel and metal-free cross-coupling reaction that leads to ipso-substitution on polycyanoarene via aryl-cyano bond cleavage. In addition, the reaction is a rare example of introducing carbon nucleophile in the photoinduced electron transfer reaction, except that of cyanide ion.     

Anti-Stokes Luminescence in Multi-Resonance-Type Thermally-Activated Delayed Fluorescence Molecules

Photon-upconversion in organic molecular systems is one of the promising technologies for future energy harvesting systems because these systems can generate excitons that possess higher energy than excitation energy. The photon-upconversion caused by absorbing ambient heat as additional energy is particularly interesting because it could ideally provide a light-driving cooling system. However, only a few organic molecular systems have been reported. Here, we report the anti-Stokes photoluminescence (ASPL) derived from hot-band absorption in a series of multi-resonance-type thermally-activated delayed fluorescence (MR-TADF) molecules. The MR-TADF molecules exhibited an anti-Stokes shift of approximately 0.1 eV with a high PL quantum yield in the solution state. The anti-Stokes shift corresponded well to the 1–0 vibration transition from the ground state to the excited singlet state, and we further evaluated a correlation between the activation energy for the ASPL intensity and the TADF process. Our demonstration underlines that MR-TADF molecules have become a novel class of ASPL materials for various future applications, such as light-driving cooling systems.     

Determination of absolute configuration of secondary alcohols using new chiral auxiliary and chemical shift calculation

A new chiral carboxylic acid 1 was synthesized for determination of absolute configuration of secondary alcohols. Several chiral alcohols were converted to esters with 1. Their experimental esterification shift changes were successfully reproduced by the chemical shift simulation method combined with molecular dynamic simulation.     

Computation of the reduction free energy of coenzyme in aqueous solution by the QM/MM-ER method

In a recent development we proposed a quantum chemical approach to compute free energy change for chemical reactions in condensed phases by combining the QM/MM method with the theory of energy representation (QM/MM-ER). We extend in this Letter the novel approach to compute reduction free energy of isoalloxazine ring of FAD (flavin adenine dinucleotide) immersed in water within the framework of the QM/MM-ER method. The characteristic feature of our approach is that the excess electron to be attached on the FAD is identified as a solute. The reduction free energy has been obtained as −80.1 kcal/mol in the aqueous solution.     

UV absorption and fluorescence properties of fused aromatic hydrocarbons having trimethylsilyl, trimethylgermyl, and trimethylstannyl groups

Effects of trimethylsilyl, trimethylgermyl, and trimethylstannyl substituents attached to fused aromatic hydrocarbons such as pyrene, anthracene, phenanthrene, and naphthalene were studied in terms of UV absorption and fluorescence properties in aerated cyclohexane solutions. Absorption maxima of trimethylsilyl-, trimethylgermyl-, and trimethylstannyl-substituted aromatic hydrocarbons shifted to longer wavelengths than those of unsubstituted ones. Absorption maxima of mono-, bis-, tris-, and tetrakis(trimethylsilyl)pyrenes shifted to longer wavelength consecutively at intervals of 10 nm. Fluorescence intensities and fluorescence lifetimes of trimethylsilyl-substituted aromatic hydrocarbons were larger and longer than those of unsubstituted ones, and they decreased in the order of Me₃SiAr > Me₃GeAr > Me₃SnAr. Fluorescence intensity of 1,3,6,8-tetrakis(trimethylsilyl)pyrene was largest among those of a series of mono-, bis-, tris-, and tetrakis(trimethylsilyl)pyrenes under aerated conditions.     

Synthesis of amino acid derived enaminones via Wolff rearrangement using vinylogous amides as carbon nucleophiles

Cyclic enaminones were synthesized in high yields from amino acids in two steps via Wolff rearrangement. The cyclization represents a rare 6-exo-dig cyclization involving a ketene as an electrophile. No racemization was observed during this reaction.     

Concise Synthesis of Potassium Acyltrifluoroborates from Aldehydes through Copper(I)‐Catalyzed Borylation/Oxidation

Potassium acyltrifluoroborates (KATs) were prepared through copper(I)‐catalyzed borylation of aldehydes and subsequent oxidation. This synthetic route is characterized by the wide range of aldehydes accessible, favorable step economy, mild reaction conditions, and tolerance of various functional groups, and it enables the facile generation of a range of KATs, for example, bearing halide, sulfide, acetal, or ester moieties. Moreover, this method was applied to the three‐step synthesis of various α‐amino acid analogues that bear a KAT moiety on the C‐terminus by using naturally occurring amino acids as the starting material.     

Effects of magnesium salts and amines on the stereoselectivity in the imine aldol reaction

In the imine aldol reactions of 1 with aromatic aldehydes using magnesium salts in the presence of amines, the threo/erythro ratios of products increased in the order Mg(ClO4)2>MgI2>MgBr2>MgCl2>Mg(OTf)2 and N,N,N',N'-tetramethylethylenediamine (TMEDA)>Et3N. This increase in the threo/erythro ratios of products was estimated to be caused by a retro-imine aldol reaction under thermodynamic control.     

Separation of perfluoroalkylsulfinic acids and perfluoroalkylsulfonic acids by ion-exclusion chromatography

Ion-exclusion chromatography has been successfully applied to the separation of a number of perfluoroalkylsulfinic acids and perfluoroalkylsulfonic acids. The separation of various perfluoroalkylsulfinic and perfluoroalkylsulfonic acids, with different alkyl groups, was investigated on a polymethacrylate-based, weakly acidic, cation-exchange resin (TSK gel OApak-A) in the H⁺-form and using conductimetric detection. When water was used as the eluent, these perfluoroalkylsulfinic and perfluoroalkylsulfonic acids could not be resolved. When an aqueous solution of benzoic acid and o-phthalic acid was used, the separation of each of these acids occurred. In order to improve their separation, the effect of the addition of methanol and 2,2,2-trifluoroethanol, as organic modifiers, was also investigated.