Synthesis of Diverse Aromatic Ketones through C−F Cleavage of Trifluoromethyl Group

An efficient synthetic method of aromatic ketones through C−F cleavage of trifluoromethyl group is disclosed. The high functional group tolerance of the transformation and the remarkable stability of trifluoromethyl group in various reactions enabled multi-substituted aromatic ketone synthesis in an efficient route involving useful transformations such as ortho-lithiation, aryne chemistry, and cross-couplings.     

Asymmetric Synthesis of α-Amino Phosphonic Acids using Stable Imino Phosphonate as a Universal Precursor

A practical method for synthesizing chiral α-amino phosphonic acid derivatives was developed. Readily available and stable N-o-nitrophenylsulfenyl (Nps) imino phosphonate was utilized as a substrate for a highly enantioselective Friedel–Crafts-type addition of indole or pyrrole nucleophiles catalyzed by chiral phosphoric acid. The resulting adduct was easily converted into N-9-fluorenylmethyloxycarbonyl (Fmoc) amino phosphonic acid, which is useful for synthesizing peptides containing an amino phosphonic acid.     

Catalytic monosilylation of 1,2-diols

The selective monosilylation of 1,2-diols catalyzed by dimethyltin dichloride was successfully developed. This procedure was applied to various 1,2-diols, giving monosilylated products in good to excellent yields with high chemoselectivity.     

Formation of cine‐Substitution Products in the Suzuki?Miyaura Cross‐Coupling Reaction Catalyzed by Dinuclear Palladium Complexes

The Suzuki? Miyaura coupling reaction catalyzed by dinuclear palladium complexes gave cine‐substitution products along with ordinary ipso‐substitution products. In the reaction in (D₆)benzene, the ipso position of the cine‐substitution product was highly deuterated. The H/D exchange also occurred in various positions of benzene rings.     

Treatment of dye wastewater by using photo-catalytic oxidation with sonication

The degradation of Acid Orange 52 in aqueous solutions was investigated by using three processes (photocatalysis, sonolysis, and photocatalysis with sonication). In the case of photocatalysis, although the concentration of Acid Orange 52 decreased to 35% in 480 min, the color of the solution was not disappeared. In the case of sonolysis, it was decomposed completely in 300 min, but the total organic carbon concentration decreased down by only about 13% in 480 min. In the case of photocatalysis with sonication, the concentration of Acid Orange 52 reached to 0 in 240 min and the total organic carbon concentration decreased by about 87% in 480 min. These results indicate that the ultrasonic irradiation enhanced the photocatalytic degradation. The addition of chloride ion (50 ppm) into Acid Orange 52 solution decreased the decomposition efficiency for photocatalysis. In the cases of sonolysis and photocatalysis with sonication, the decomposition efficiency did not change significantly by the addition of chloride ion. These results indicate that chloride ion disturbs the photocatalysis of dye, but the decomposition of dye using the irradiation of ultrasound is not influenced by chloride ion. From these results, it is considered that the photocatalysis with sonication is most effective for the decomposition of dye in the three processes in this study.     

Molecular recognition by a novel boronate-containing CTG derivative for hydroxyanthraquinones

C₃-functionalized cyclotriguaiacylene (CTG) derivatives were employed in the development of highly selective recognition compounds due to their unique molecular structures. Here, a novel C₃-functionalized CTG containing boronate (PPB-CTG) was synthesized and its molecular recognition ability for hydroxyanthraquinones was investigated by fluorescence spectroscopy. The addition of the synthesized PPB-CTG led to a large increase in the fluorescence intensity of only alizarin and not 1-hydroxyanthraquinone, 2-hydroxyanthraquinone nor quinizarin. It was, thus, suggested that the cyclotriveratrylene (CTV) structure plays an important role in the recognition ability toward alizarin since the mono-phenyl boronate compound (m-TPBAP) showed poor fluorescence properties toward alizarin. Moreover, it was found that the 1:1 mixture of PPB-CTG and alizarin was effective as a fluorescence-enhanced probe toward fluoride ions.     

Enantiodivergent Atroposelective Synthesis of Chiral Biaryls by Asymmetric Transfer Hydrogenation: Chiral Phosphoric Acid Catalyzed Dynamic Kinetic Resolution

Reported herein is an enantiodivergent synthesis of chiral biaryls by a chiral phosphoric acid catalyzed asymmetric transfer hydrogenation reaction. Upon treatment of biaryl lactols with aromatic amines and a Hantzsch ester in the presence of chiral phosphoric acid, dynamic kinetic resolution (DKR) involving a reductive amination reaction proceeded smoothly to furnish both R and S isomers of chiral biaryls with excellent enantioselectivities by proper choice of hydroxyaniline derivative. This trend was observed in wide variety of substrates, and various chiral biphenyl and phenyl naphthyl adducts were synthesized with satisfactory enantioselectivities in enantiodivergent fashion. The enantiodivergent synthesis of synthetically challenging, chiral o‐tetrasubstituted biaryls were also accomplished, and suggests high synthetic potential of the present method.