α-Fluoroamine synthesis via P(III)-mediated deoxygenative geminal fluorosulfonimidation of 1,2-diketones.

A deoxygenative geminal fluorosulfonimidation of 1,2-diketones was achieved for the synthesis of tetrasubstituted α-fluoroamines under mild conditions. In this study, a transition metal-free formal N-F insertion of N-fluorobenzenesulfonimide was enabled via the Kukhtin-Ramirez reaction employing a dealkylation-resistant P(III) reagent developed in our laboratory. Computational analysis was also performed to obtain a general mechanistic picture, which explained the reactivity and selectivity for this type of reaction.

Access to Multifunctionalized Tetrasubstituted Carbon Centers Bearing up to Three Different Heteroatoms via Tandem Geminal Chlorofluorination of 1,2-Dicarbonyl Compounds.

The incorporation of noncarbon heteroatoms into organic molecules typically instills characteristic and often valuable functionalities. The copresence of different heteroatoms can further broaden their utility through the synergistic cooperative effects, which may even lead to the discovery of formerly unavailable properties that are not just a simple accumulation of each function. However, despite increasing interest in the controllable installation of heteroatoms, it has been extremely challenging to construct carbon centers having three different heteroatoms in a synthetically useful manner. In this work, our group's tandem geminal chlorofluorination (Cl, F) strategy was applied to rationally designed heteroatom-bearing 1,2-dicarbonyl substrates, including α-keto thioesters (S), α-keto N-acylindoles (N), and α-keto acylsilane (Si), which resulted in the practical production of doubly or triply heterofunctionalized tetrasubstituted carbon centers with excellent site-selectivity.

Phosphorus(III)-Mediated, Tandem Deoxygenative Geminal Chlorofluorination of 1,2-Diketones.

Tetrasubstituted carbon containing two different halogen substituents was constructed in a single-step operation by utilizing the carbene-like reactivity of dioxaphospholene through the tandem reaction of electrophilic and nucleophilic halogenating reagents. It was crucial to devise non-dealkylatable phosphoramidite, which enabled the efficient formation of geminal chlorofluorides from various 1,2-diketones with (PhSO2)2NF and n-Bu4NCl. In addition, selective functionalization of the chlorine substituent was demonstrated, and the absence of halogen scrambling was confirmed.

Ultrafast intramolecular proton transfer reactions and solvation dynamics of DMSO.

Ultrafast intramolecular proton transfers of 1,2-dihydroxyanthraquinone (alizarin-h2) and its deuterated product (alizarin-d2) in dimethyl sulfoxide (DMSO) have been investigated by femtosecond stimulated Raman spectroscopy. The population dynamics in the solute vibrational mode of νC=O and the coherent oscillations observed in all of the skeletal vibrational modes νC=O and νC=C clearly showed the ultrafast excited-state intramolecular proton transfer dynamics of 110 and 170 fs for alizarin-h2 and alizarin-d2, respectively. Interestingly, we have observed that the solvent vibrational modes νS=O and νCSC may also represent ultrafast structural dynamics at the frequencies for its "free" or "aggregated" species. From the kinetic analysis of the νS=O and νCSC modes of DMSO, the ultrafast changes in the solvation or intermolecular interactions between DMSO molecules initiated by the structural changes of solute molecules have been thoroughly investigated. We propose that the solvent vibrational modes νS=O and νCSC of DMSO can be used as a "sensor" for ultrafast chemical reactions accompanying the structural changes and subsequent solute-solvent interactions.

Comparative analysis of endogenous hormones level in two soybean (Glycine max L.) lines differing in waterlogging tolerance.

Waterlogged condition due to flooding is one of the major abiotic stresses that drastically affect the soybean growth and yield around the world. As a result, many breeders have focused on the development of waterlogging tolerance in soybean varieties, and thus, several tolerant varieties were developed. However, the physiological mechanism of waterlogging tolerance is not yet fully understood. We particularly studied the endogenous hormones regulation during waterlogging in two contrasting soybean genotypes. According to our results, adventitious roots were better developed in the waterlogging tolerant line (WTL) than in the waterlogging susceptible line (WSL). Endogenous hormones also showed significant differences between WTL and WSL. The ethylene production ratio was higher in WTL than in WSL, and methionine was higher in WTL than in WSL. Other endogenous abscisic acid (ABA) contents were lower in WTL than in WSL. Conversely, gibberellic acid (GA) showed a tendency to be high in WTL, especially the levels of the bioactive GA4. The ratio of total GA and ABA was significantly higher in WTL than in WSL. Anatomical study of the root revealed that aerenchyma cells in the stele were better developed in WTL than in WSL.

Effects of HPE-101, a skin penetration enhancer, on human erythrocyte membranes.

The primary aim of this study was to investigate the skin permeation-enhancing mechanism of HPE-101 using erythrocyte ghost cells prepared from human whole blood as a biomembrane model. The extent of hemolysis of erythrocytes induced by HPE-101 was measured using a spectrophotometer at 540nm. The effect of HPE-101 on lipid fluidity was examined by observing the change of intramolecular excimer formation and fluorescence polarization using an intramolecular probe (1,3-bis(pyrene) propane) and a lipid probe (1,6-diphenyl 1,3,5-hexatriene), respectively. Hemolysis of erythrocytes was observed at 0.01mM and completed at 1.0mM of HPE-101. The fluorescence polarization of the ghost membrane decreased with the addition of HPE-101, whereas the intramolecular excimer formation increased. HPE-101 thus enhanced the rotational mobility and the lateral diffusion, thereby decreasing the microviscosity of ghost membranes, implying that HPE-101 increases the lipid fluidity of ghost membranes. Therefore, HPE-101 seems to cause an increase in fluidity of the lipid bilayers in the stratum corneum of the skin, resulting in the reduction of diffusion resistance.