An economical approach for peptide synthesis via regioselective C–N bond cleavage of lactams

An economical, solvent-free, and metal-free method for peptide synthesis via C–N bond cleavage using lactams has been developed. The method not only eliminates the need for condensation agents and their auxiliaries, which are essential for conventional peptide synthesis, but also exhibits high atom economy. The reaction is versatile because it can tolerate side chains bearing a range of functional groups, affording up to >99% yields of the corresponding peptides without racemisation or polymerisation. Moreover, the developed strategy enables peptide segment coupling, providing access to a hexapeptide that occurs as a repeat sequence in spider silk proteins.

An economical, solvent-free, and metal-free method for peptide synthesis via C–N bond cleavage using lactams has been developed.     

Synthesis of 3-substituted isocoumarins and their inhibitory effects on degranulation of RBL-2H3 cells induced by antigen

Eleven 3-substituted isocoumarins and a benzylidenephthalide were synthesized through thermal cyclization reaction of delta- and gamma-ketoamides, respectively. Subsequent deprotection of the hydroxyl groups of the resulting isocoumarin and benzylidenephthalide compounds afforded thunberginols A, B, and F, respectively, which originated from the processed leaves of Hydrangea macrophylla SERINGE var. thunbergii MAKINO. The synthesized isocoumarins and thunberginols were evaluated for their anti-allergic activity, in which thunberginol B exhibited the highest inhibitory potency on the degranulation of RBL-2H3 cells induced by antigen. Structure-activity relationship studies were carried out to determine the necessary substituents on the 3-phenylisocoumarin skeleton for inhibitory activity.     

Tungsten‐Catalyzed Regio‐ and Enantioselective Aminolysis of trans‐2,3‐Epoxy Alcohols: An Entry to Virtually Enantiopure Amino Alcohols

The first catalytic enantioselective aminolysis of trans‐2,3‐epoxy alcohols has been accomplished. This stereospecific ring‐opening process was efficiently promoted by a tungsten/bis(hydroxamic acid) catalytic system, furnishing various anti‐3‐amino‐1,2‐diols with excellent regiocontrol and high enantioselectivities (up to 95 % ee). Moreover, virtually enantiopure 3‐amino‐1,2‐diols could be obtained by the sequential combination of two reactions that both involve the use of a chiral catalyst.     

Acidic properties of V2O5-WO3/ZrO2 catalysts

The adsorption of pyridine on V₂O₅−WO₃/ZrO₂ has been studied by FTIR. In V₂O₅/ZrO₂ (2 wt.%), the number of both Br?nsted and Lewis acidic sites increased with the addition of WO₃, while in V₂O₅/ZrO₂ (5 wt.%), Br?nsted sites increased and Lewis sites did not change.     

Nitrosation of Phenolic Substrates under Mildly Basic Conditions: Selective Preparation of p-Quinone Monooximes and Their Antiviral Activities

Nitrosation of 3-methoxyphenol and 1-naphthol were examined under both acidic (NaNO(2)-EtCO(2)H-H(2)O) and basic (i-AmNO(2)-K(2)CO(3)-DMF) conditions. Acidic nitrosations afforded ortho-directed products, whereas para-directed nitrosations were observed under basic conditions to yield p-quinone monooximes. The basic para-directed nitrosation was further examined using 15 phenols, two naphthols, and four phenolic heterocyclics. A one-pot operation of the basic nitrosation followed by methylation with dimethyl sulfate gave the corresponding methyl ethers in high yield. Two p-quinone monooximes derived from 3-methoxyphenol and 8-hydroxyquinoline showed a moderate activity against HSV-1, and the latter oxime was also effective against HSV-2. On the other hand, p-quinone monooximes derived from methyl salicylate, 1-naphthol, 7-hydroxy-2-methylbenzo[b]furan, and 8-hydroxycoumarin showed the comparable activity to that of DDI against HIV-1.     

Development and application of versatile bis-hydroxamic acids for catalytic asymmetric oxidation

In this article, we describe the development and preliminary results of our new designed C₂-symmetric bis-hydroxamic acid (BHA) ligands and the application of the new ligands for vanadium-catalyzed asymmetric epoxidation of allylic alcohols as well as homoallylic alcohols. From this success we demonstrate the versatile nature of BHA in the molybdenum catalyzed asymmetric oxidation of unfunctionalized olefins and sulfides.     

Optical-Optical Double Resonance Spectroscopy of the 1g(P1)-AΠ (1u)-XΣg Transition of I2

Optical-optical double resonance spectroscopy was used to study the 1_g(³P₁) ion-pair state of I₂ correlating to I⁻(¹S)+I⁺³P₁) at the dissociation limit. We gained access to the 1_g(³P₁) state though the A³Π (1_u) state in the (1+1) photon-excitation scheme. The pump laser excited the A³Π (1_u)-X¹Σ_g⁺ transition at a fixed frequency for state selection. The probe laser was scanned to detect the 1_g(³P₁)-A³Π (1_u) resonance by monitoring the ultraviolet emission from the 1_g(³P₁) state at 278 nm. The 1_g(³P₁) state was observed in a vibrational progression consisting of P and R doublets. An energy level analysis was carried out for the 1_g(³P₁) state in the 0≤ v ≤ 14 and 12≤J≤135 range, which led to a set of molecular parameters including the Ω-doubling constant. The Ω-doubling of the 1_g(³P₁) state was discussed by the pure precession model and interpreted to occur through the heterogeneous coupling with the 0_g⁻(³P₁) state correlating to the same ionic asymptote.     

Thickness and Surface Profile Measurement by a Sinusoidal Wavelength-Scanning Interferometer

We propose a sinusoidal wavelength-scanning interferometer for measuring thickness and surface profile of a thin film. The interference signal contains phase modulation amplitude Z and phase $aL which are related to the positions and profiles of the reflecting surfaces, respectively. By reducing the difference between the detected signal and the estimated signal using the multidimensional nonlinear least-squares algorithm, we estimate values of Z and $aL. Experimental results show that the front and rear surfaces of a silica glass plate of 20 $mUm-thickness could be measured with an error less than 10 nm.     

A regioselective enolate formation of trimethylsilylmethyl ketones application to the (E)-selective synthesis of α,β-unsaturated ketones

Two possible enolate anions of trimethylsilylmethyl ketones have been prepared regioselectively by the appropriate choice of base. The one directed to the silylmethyl site behaves as a highly reactive and (E)-selective condensation reagent to aldehydes.     

Sugar-water interaction from diffusion measurements

The diffusion coefficients of deoxyribose and ribose in water were measured at 25°C. The Stokes-Einstein relation for mono-, di-, and tri-saccharides are discussed. The diffusion coefficient at infinite dilution D_o for deoxyribose was the largest among these sugars. It appears that the deoxyribose breaks local water structure but the ribose hardly affects the structure. D_o correlates well with the mean number of e-OH groups in the sugar molecule. It is suggested that the mean number of e-OH groups is a good parameter to describe the properties of sugar hydration.