NMR‐based analysis of the chemical composition of Japanese persimmon aqueous extracts

Japanese persimmon (Diospyros kaki L.) is recognized as an outstanding source of biologically active compounds relating to many health benefits. In the present study, NMR spectroscopy provided a comprehensive metabolic overview of Japanese persimmon juice. Detailed signal assignments of Japanese persimmon juice were carried out using various 2D NMR techniques incorporated with broadband water suppression enhanced through T₁ effects (BB‐WET) or WET sequences, and 26 components, including minor components, were identified. In addition, most components were quantitatively evaluated by the integration of signals using conventional ¹H NMR and BB‐WET NMR. This is the first detailed analysis combined with quantitative characterization of chemical components using NMR for Japanese persimmon. Copyright © 2015 John Wiley & Sons, Ltd.     

Regioselective Alkylative Carboxylation of Allenamides with Carbon Dioxide and Dialkylzinc Reagents Catalyzed by an N‐Heterocyclic Carbene–Copper Complex

The alkylative carboxylation of allenamide catalyzed by an N‐heterocyclic carbene (NHC)–copper(I) complex [(IPr)CuCl] with CO₂ and dialkylzinc reagents was investigated. The reaction of allenamides with dialkylzinc reagents (1.5 equiv) and CO₂ (1 atm.) proceeded smoothly in the presence of a catalytic quantity of [(IPr)CuCl] to afford (Z)‐α,β‐dehydro‐β‐amino acid esters in good yields. The reaction is regioselective, with the alkyl group introduced onto the less hindered γ‐carbon, and the carboxyl group introduced onto the β‐carbon atom of the allenamides. The first step of the reaction was alkylative zincation of the allenamides to give an alkenylzinc intermediate followed by nucleophilic addition to CO₂. A variety of cyclic and acyclic allenamides were found to be applicable to this transformation. Dialkylzinc reagents bearing β‐hydrogen atoms, such as Et₂Zn or Bu₂Zn, also gave the corresponding alkylative carboxylation products without β‐hydride elimination. The present methodology provides an easy route to alkyl‐substituted α,β‐dehydro‐β‐amino acid ester derivatives under mild reaction conditions with high regio‐ and stereoselectivtiy.     

Molecular Insights into the Ligand-Based Six-Proton- and Six-Electron-Transfer Processes Between Tris-ortho-Phenylenediamines and Tris-ortho-Benzoquinodiimines

The global demand for energy and the concerns over climate issues renders the development of alternative renewable energy sources such as hydrogen (H₂) important. A high-spin (hs) Fe^II complex with o-phenylenediamine (opda) ligands, [Fe^II(opda)₃]²⁺ (hs- [6R] ²⁺), was reported showing photochemical H₂ evolution. In addition, a low-spin (ls) [Fe^II(bqdi)₃]²⁺ (bqdi: o-benzoquinodiimine) (ls- [0R] ²⁺) formation by O₂ oxidation of hs- [6R] ²⁺, accompanied by ligand-based six-proton and six-electron transfer, revealed the potential of the complex with redox-active ligands as a novel multiple-proton and -electron storage material, albeit that the mechanism has not yet been understood. This paper reports that the oxidized ls- [0R] [PF₆]₂ can be reduced by hydrazine giving ls-[Fe^II(opda)(bqdi)₂][PF₆]₂ (ls- [2R] [PF₆]₂) and ls-[Fe^II(opda)₂(bqdi)][PF₆]₂ (ls- [4R] [PF₆]₂) with localized ligand-based proton-coupled mixed-valence (LPMV) states. The first isolation and characterization of the key intermediates with LPMV states offer unprecedented molecular insights into the design of photoresponsive molecule-based hydrogen-storage materials.     

Total Synthesis of Taxol Enabled by Inter- and Intramolecular Radical Coupling Reactions

Taxol is a clinically used drug for the treatment of various types of cancers. Its 6/8/6/4-membered ring (ABCD-ring) system is substituted by eight oxygen functional groups and flanked by four acyl groups, including a β-amino acid side chain. Here we report a 34-step total synthesis of this unusually oxygenated and intricately fused structure. Inter- and intramolecular radical coupling reactions connected the A- and C-ring fragments and cyclized the B-ring, respectively. Functional groups of the A- and C-rings were then efficiently decorated by employing newly developed chemo-, regio-, and stereoselective reactions. Finally, construction of the D-ring and conjugation with the β-amino acid delivered taxol. The powerful coupling reactions and functional group manipulations implemented in the present synthesis provide new valuable information for designing multistep target-oriented syntheses of diverse bioactive natural products.     

Asymmetric Synthesis of a Quaternary Carbon Stereogenic Center by Organocatalysis Using a Primary Amino Acid and Its Salt

In this personal account, our recent developments on the asymmetric synthesis of a quaternary carbon stereogenic center by organocatalysis using a primary amino acid and its salt as a catalyst are described in three chapters: (1) conjugate addition to nitroalkenes and vinyl ketones, (2) nucleophilic addition to π-allyl palladium complexes, and (3) nucleophilic substitution reactions with allyl and propargyl halides. By these methods, asymmetric α-allylation of α-branched aldehydes and ketones smoothly proceeded to give γ-nitroaldehydes, ketoaldehydes, α-allylated aldehydes, and α-allylated β-ketoesters possessing a quaternary carbon stereogenic center in good yields with high enantioselectivities.     

Multicomponent Molecular Orbital–Climbing Image–Nudged Elastic Band Method to Analyze Chemical Reactions Including Nuclear Quantum Effect

To analyze the H/D isotope effects on hydrogen transfer reactions in XHCHCHCHY?XCHCHCHYH (X, Y=O, NH, or CH₂) including the nuclear quantum effect of proton and deuteron, we propose a multicomponent molecular orbital‐climbing image‐nudged elastic band (MC_MO–CI–NEB) method. We obtain not only transition state structures but also minimum‐energy paths (MEPs) on the MC_MO effective potential energy surface by using MC_MO–CI–NEB method. We find that nuclear quantum effect affects not only stationary‐point geometries but also MEPs and electronic structures in the reactions. We clearly demonstrate the importance of including nuclear quantum effects for H/D isotope effect on rate constants (k_H/k_D).     

Upper limit of enhancement of boiling heat transfer in a narrow vertical rectangular channel due to passing bubbles

An experimental study has been made of saturated boiling heat transfer for water and R113 in a narrow vertical rectangular channel (2 mm space, 20 mm wide, and 200 mm long) at atmospheric pressure, in which the vertical heated surface (10 mm long and 20 mm wide) is located on one side at a position of 150 mm from its entrance and bubbles are forcibly passed through it at a designated period from 0.33 to 1.0 sec. The experiment shows that the heat transfer coefficients are increased by the bubble passing through the heated surface for the value of thermal diffusivity,a, times period, T₀, of the passing bubbles above about 6×10^–9 m² (a T ₀>6×10^–9 m²) while fora T ₀< 6×10^–9 m², the heat transfer coefficients become independent of the period and the effectiveness of the enhancement of the heat transfer owing to the passing bubble disappears.

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Die obere Grenze der Verbesserung des Wärmeübergangs beim Sieden in einem vertikalen, rechteckigen Kanal infolge von aufsteigenden Blasen

Zusammenfassung Es wurden Experimente über den Wärmeübergang beim Sättigungssieden mit Wasser und R113 in einem engen, vertikalen, rechteckigen Kanal (2 mm Abstand, 20 mm Breite und 200 mm Länge) bei Umgebungsdruck durchgeführt, wobei die vertikale, beheizte Oberfläche (10 mm lang und 20 mm breit) auf der einen Seite in einem Abstand von 150 mm vom Eintritt angeordnet ist und die Blasen zwangsweise durch den Kanal sich mit einem Periodenabstand von 0,033 bis 1,0 s bewegen. Das Experiment zeigt, daß die Wärmeübergangskoeffizienten durch das Vorbeistreichen der Blasen an der beheizten Oberfläche verbessert werden, wenn das Produkt aus Temperaturleitfähigkeit,a, mal der Periode, T₀, der vorbeistreichenden Blasen größer als 6×10^–9 m² liegt, während unterhalb dieses Wertes der Wärmeübergangskoeffizient unabhängig von der Blasenperiode ist und die Effektivität der Wärmeübergangsverbesserung infolge der Blasenströmung verschwindet.

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Nomenclature a thermal diffusivity of liquid - ¯h time-averaged heat transfer coefficient - q _w heat flux at wall - T ₀ period of passing bubble - T _w(t) temperature of heated surface - T _w amplitude of heated surface temperature Greek symbols thermal conductivity - thickness of liquid film     

Preparation of Ring and Chain Condensed Oligophosphates

Preparations of small-ring and short-chain condensed phosphates were made by dry and wet processes, respectively. The crystallization of tetra- hexa-, and octaphosphates from the phosphate solution was not easy, and metal salts of these oligophosphates were amorphous and unstable at normal temperature. Guanidine tetraphosphate and ammonium hexaphosphate were crystalline and stable at normal temperature.     

CdS and Cd carboxylate nanoclusters dispersed in polymer matrix produced by a freeze drying method

Cadmium sulfide (CdS) nanoclusters were prepared by a freeze drying method from two types of cadmium carboxylates. One was cadmium methacrylates that were part of poly(methyl methacrylate) (PMMA) ionomer. The other was cadmium acetates that were dispersed in PMMA. X-ray diffraction was mainly used to study the formation and the size of nanoclusters. The size of CdS made from the ionomer was 0.9 nm, whereas that from the composite of cadmium acetate and PMMA was 2 nm. This was consistent with the size difference of the precursors of CdS: i.e., Cd carboxylate nanoclusters (ionic aggregates) were smaller in the ionomer than in the PMMA mixture, because ionic groups in the ionomer were constrained due to their connectivity to backbone chains and thus forming smaller ionic aggregates. Once stabilized, however, CdS nanocluster sizes were unchanged despite thermal treatments at up to 220 °C for 24 h for both systems. Structural transformations from a freeze dried cadmium carboxylate powder, to a CdS-containing powder, and to a heat-treated CdS-containing sample are speculated for both types of systems.