Reconstruction of the 2014 eruption sequence of Ontake Volcano from recorded images and interviews

A phreatic eruption at Mount Ontake (3067 m) on September 27, 2014, led to 64 casualties, including missing people. In this paper, we clarify the eruption sequence of the 2014 eruption from recorded images (photographs and videos obtained by climbers) and interviews with mountain guides and workers in mountain huts. The onset of eruption was sudden, without any clear precursory surface phenomena (such as ground rumbling or strong smell of sulfide). Our data indicate that the eruption sequence can be divided into three phases. Phase 1: The eruption started with dry pyroclastic density currents (PDCs) caused by ash column collapse. The PDCs flowed down 2.5 km SW and 2 km NW from the craters. In addition, PDCs moved horizontally by approximately 1.5 km toward N and E beyond summit ridges. The temperature of PDCs at the summit area partially exceeded 100 °C, and an analysis of interview results suggested that the temperature of PDCs was mostly in the range of 30–100 °C. At the summit area, there were violent falling ballistic rocks. Phase 2: When the outflow of PDCs stopped, the altitude of the eruption column increased; tephra with muddy rain started to fall; and ambient air temperature decreased. Falling ballistic rocks were almost absent during this phase. Phase 3: Finally, muddy hot water flowed out from the craters. These models reconstructed from observations are consistent with the phreatic eruption models and typical eruption sequences recorded at similar volcanoes.ArticleEarth, Planets and Space. 68:79 (2016)journal articl

Amino Amide Organocatalysts for Asymmetric Michael Addition of β-Keto Esters with β-Nitroolefins

Asymmetric Michael addition of β-keto esters with trans-β-nitroolefins using chiral amino amide organocatalyst was tried and afforded synthetically useful chiral Michael adducts in both excellent chemical yields (up to 99%) and stereoselectivities (up to dr. 99:1, up to 98% ee)

Hybrid-Type Squaramide-Fused Amino Alcohol Organocatalysts for Enantioselective Nitro-Aldol Reaction of Nitromethane with Isatins

A series of new hybrid type squaramide-fused amino alcohol (SFAA) catalysts were synthesized and their catalytic efficiency in enantioselective nitro-aldol reaction of various isatins with nitromethane that afford the chiral 3-substituted 3-hydroxyoxindoles in excellent chemical yields (up to 99%) and high enantioselectivities (up to 95% ee) is described. The resulting chiral 3-hydroxyoxindoles could be used as synthetic precursors for the synthesis of several natural products with a broad spectrum of fascinating biological activities

Reconstruction of a phreatic eruption on 27 September 2014 at Ontake volcano, central Japan, based on proximal pyroclastic density current and fallout deposits

The phreatic eruption at Ontake volcano on 27 September 2014, which caused the worst volcanic disaster in the past half-century in Japan, was reconstructed based on observations of the proximal pyroclastic density current (PDC) and fallout deposits. Witness observations were also used to clarify the eruption process. The deposits are divided into three major depositional units (Units A, B, and C) which are characterized by massive, extremely poorly sorted, and multimodal grain-size distribution with 30–50 wt% of fine ash (silt–clay component). The depositional condition was initially dry but eventually changed to wet. Unit A originated from gravity-driven turbulent PDCs in the relatively dry, vent-opening phase. Unit B was then produced mainly by fallout from a vigorous moist plume during vent development. Unit C was derived from wet ash fall in the declining stage. Ballistic ejecta continuously occurred during vent opening and development. As observed in the finest population of the grain-size distribution, aggregate particles were formed throughout the eruption, and the effect of water in the plume on the aggregation increased with time and distance. Based on the deposit thickness, duration, and grain-size data, and by applying a scaling analysis using a depth-averaged model of turbulent gravity currents, the particle concentration and initial flow speed of the PDC at the summit area were estimated as 2 × 10−4–2 × 10−3 and 24–28 m/s, respectively. The tephra thinning trend in the proximal area shows a steeper slope than in similar-sized magmatic eruptions, indicating a large tephra volume deposited over a short distance owing to the wet dispersal conditions. The Ontake eruption provided an opportunity to examine the deposits from a phreatic eruption with a complex eruption sequence that reflects the effect of external water on the eruption dynamics.ArticleEarth, Planets and Space. 68: 82(2016)journal articl

Chiral primary amino alcohol organobase catalyst for the asymmetric Diels-Alder reaction of anthrones with maleimides

Simple chiral TES-amino alcohol organocatalysts containing a bulkysilyl [triethylsilyl: TES] group on oxygen atom at γ-position were designed andsynthesized as new organocatalysts for the enantioselective Diels-Alder (DA) reactionof anthrones with maleimides to produce chiral hydroanthracene DA adducts (up to99% yield with up to 94% ee)

Lipase-catalyzed domino Michael-aldol reaction of 2-methyl-1,3-cycloalkanedione and methyl vinyl ketone for the synthesis of bicyclic compounds

Synthesis of bicyclic compounds was achieved via a lipase-catalyzed, stereoselective, domino Michael–aldol reaction of 2-methyl-1,3-cycloalkanedione and methyl vinyl ketone. Appropriate reaction conditions, including the type of enzyme, solvent, and temperature, were determined. In addition, the effects of solvent polarity and addtives were investigated. The reaction proceeded in the presence of lipase AS in a solution of 20% acetone in dimethylsulfoxide (DMSO) at 10 °C for 8 days, followed by the addition of p-toluenesulfonic acid (TsOH) to afford bicyclic compounds in 51–83% yields with moderate stereoselectivity. Although this domino Michael–aldol reaction showed only moderate stereoselectivity, even with the acid-supported enhancement of the reaction, these results represent potential new applications for lipase

A novel chiral oxazolidine organocatalyst for the synthesis of an oseltamivir intermediate using a highly enantioselective Diels-Alder reaction of 1,2-dihydropyridine

Enantioselective Diels-Alder reactions of 1,2-dihydropyridines with acroleins using a novel chiral oxazolidine organocatalyst afforded chiral isoquinuclidines that is an efficient synthetic intermediate of oseltamivir, with fairly good chemical yield and excellent enantioselectivity (90%, up to >99% ee)

An efficient synthesis of chiral isoquinuclidines by Diels-Alder reaction using Lewis acid catalyst

The Diels-Alder reaction of 1,2-dihydropyridine derivatives (1-phenoxycarbonyl-1,2-dihydropyridine 1 or 1-methoxycarbonyl-1,2-dihydropyridine 4) with N-acryloyl (1S)-2,10-camphorsultam (1S)-2 (or N-acryloyl (1R)-2,10-camphorsultam (1R)-2) in the presence of Lewisacid such as titanium tetrachloride, zirconium tetrachloride, and hafnium tetrachloride afforded the endo-cycloaddition product, 2-azabicyclo[2.2.2]octane derivatives in good yields with excellent diastereoselectivity. The absolute stereochemistry assignment of the endo-cycloaddition product (1S)-5a starting from N-acryloyl (1S)-2,10-camphorsultam (1S)-2hasbeen established to be (1S, 4R, 7S) and the reaction mechanism was proposed

New Hybrid-type Squaramide-Fused Amino Alcohol Organocatalyst for Enantioselective Domino Michael Addition/Cyclization Reaction of Oxoindolines with Cyclic 1,3-Diketones

The new hybrid-type squaramide-fused amino alcohol containing both a Bronsted basic site and hydrogen bondingsites in the molecule showed a high catalytic activity as an l organocatalyst in the enantioselective domino Michael addition/cyclization reaction of oxoindohnes with cyclic 1,3-etones to afford\u27the chiralsproonjugate oxindoles featuring 2-aminopyrans fusing with l carbo-heterocyclic ring systems with l excellent chemical yields (up Ito 98%) and enantioselectivities (up to 95% ee). The obtained chiral spiroconjugated 2-aminopyrans bearing quaternary stereogenic carbon center could be used as l synthetic precursors for several natural products that ave a broad spectrum Iof fascinating biological activities

Biotransformation of organic compounds in vivo using larvae of beetles (Allomyrina dichotoma) as biocatalysts

The biotransformation of organic compounds using the larvae of the Japanese rhinoceros beetle (Allomyrina dichotoma) as a biocatalyst is described. When phenyl alkanediones were administered by mouth (p.o) or subcutaneous injection (s.c) to the beetle, asymmetric reduction occurred to yield the corresponding diols in varying optical yields: 1-phenyl-1,2-propandione or 1-phenyl-1,3-butanedione reduced to (1R,2S)- and (1S,2S)-1,2-phenylpropanediols in high optical yields or (1R,3S)- and (1R,3R)-1-phenyl-1,3-butanediols in low to high optical yields, respectively. By administrating 1-phenyl-1-propanone, 1-phenyl-1-butanone or 4-phenyl-2-butanone, redox reactions occurred to give 1-phenyl-1,2-propanediols or 1-phenyl-1,3-butanediols in lower optical yields. The administrations of β-ionone and cinnamyl chloride resulted in regioselective allylic oxidations producing enone and cinnamic acid, respectively. However, when (R)-(-)-carvone was administered, regiospecific dihydroxylation at the isopropenyl group occurred to give (4R,8R)- and (4R,8S)-8,9-dihydroxy-8,9-dihydrocarvone as diastereoisomers. These results appear to demonstrate similar reaction tendency with the case of a microorganism. It is possible that these reactions were due in part to bacteria in the intestine of the larva: however, regio- and stereoselectivities of the reactions were sometimes unique. Thus, it is supposed that these biotransformations were accomplished by the ensemble of the larva׳s own enzymes with several bacteria. The results obtained in this study might show the possibility of using such enzymes derived from insects, including beetle larvae, as a biocatalyst