Highly Selective Perfluoroalkylation of Unsaturated Molecules upon Photoirradiation in BTF as an Organic/Fluorous Hybrid Solvent

Benzotrifluoride (BTF), an eco-friendly solvent, can dissolve many organic and fluorous molecules because of the organic and fluorous motifs in its structure. Using BTF as solvent, we have developed a series of reactions for perfluoroalkylation of various unsaturated compounds upon photoirradiation with a Xe lamp through Pyrex. For example, alkynes, allenes, vinylcyclopropanes, isocyanides, diynes, dienes, and enynes successfully undergo regioselective perfluoroalkyliodination, perfluoroalkylselenation, and perfluoroalkyltelluration in BTF. In addition, the present photoinitiation procedure can be applied to trifluoromethylatio

Regioselective Hydrothiolation of Alkenes Bearing Heteroatoms with Thiols Catalyzed by Palladium Diacetate

In sharp contrast to many examples of transition-metal-catalyzed hydrothiolation of alkynes, the corresponding catalytic addition of thiols to alkenes has remained undeveloped. However, a novel Pd-catalyzed addition of thiols to alkenes bearing a heteroatom, such as oxygen and nitrogen, is found to proceed under mild conditions to give the corresponding Markovnikov adducts, regioselectively, in good yields

Optimization of simultaneous saccharification and fermentation conditions with amphipathic lignin derivatives for concentrated bioethanol production

Amphipathic lignin derivatives (A-LDs) prepared from the black liquor of soda pulping of Japanese cedar are strong accelerators for bioethanol production under a fed-batch simultaneous enzymatic saccharification and fermentation (SSF) process. To improve the bioethanol production concentration, conditions such as reaction temperature, stirring program, and A-LDs loadings were optimized in both small scale and large scale fed-batch SSF. The fed-batch SSF in the presence of 3.0 g/L A-LDs at 38 degrees C gave the maximum ethanol production and a high enzyme recovery rate. Furthermore, a jar-fermenter equipped with a powerful mechanical stirrer was designed for 1.5 L-scale fed-batch SSF to achieve rigorous mixing during high substrate loading. Finally, the 1.5 L fed-batch SSF with a substrate loading of 30% (w/v) produced a high ethanol concentration of 87.9 g/L in the presence of A-LDs under optimized conditions

Selective Thiolative Lactonization of Internal Alkynes Bearing a Hydroxyl Group with Carbon Monoxide and Organic Disulfides Catalyzed by Transition-Metal Complexes

Although many transition-metal catalysts are ineffective for the addition and carbonylative addition of organic disulfides to internal alkynes, dicobalt octacarbonyl and palladium complexes such as Pd­(PPh₃)₄ and Pd­(OAc)₂ were found to exhibit excellent catalytic activity for the thiolative lactonization of internal alkynes bearing a hydroxyl group. In the presence of the cobalt or palladium catalyst, internal alkynes bearing a hydroxy group, such as homopropargyl alcohol derivatives, successfully undergo thiolative carbonylation with carbon monoxide and an organic disulfide regio- and stereoselectively to afford the corresponding thio group bearing-lactones in good yields. In the Co-catalyzed reaction, the cobalt–alkyne complex from dicobalt octacarbonyl and internal alkyne acts as a key species, making it possible to attain thiolative lactonization of internal alkynes with a hydroxyl group. In the Pd-catalyzed reaction, the coordination of the hydroxy group to the palladium catalyst plays an important role for the thiolative lactonization

Gold-Catalyzed <i>Anti</i>-Markovnikov Selective Hydrothiolation of Unactivated Alkenes

Despite the widespread use of transition-metal catalysts in organic synthesis, transition-metal-catalyzed reactions of organosulfur compounds, which are known as catalyst poisons, have been difficult. In particular, the transition-metal-catalyzed addition of organosulfur compounds to unactivated alkenes remains a challenge. A novel gold-catalyzed hydrothiolation of unactivated alkenes is presented, which proceeds effectively to give the <i>anti</i>-Markovnikov-selective adducts in good yields and in a regioselective manner

Palladium-Catalyzed Markovnikov-Selective Hydroselenation of <i>N</i>‑Vinyl Lactams with Selenols Affording <i>N</i>,<i>Se</i>-Acetals

The highly regioselective hydroselenation of <i>N</i>-vinyl lactams has been revealed to successfully afford the corresponding <i>N</i>,<i>Se</i>-acetals as Markovnikov adducts. In the case of terminal <i>N</i>-vinyl lactams, Markovnikov-selective hydroselenation proceeds efficiently in the absence of any catalyst (or additive), owing to the acidity of the selenols. In contrast, the self-promoted hydroselenation is inefficient with internal <i>N</i>-vinyl lactams. In the presence of palladium diacetate (Pd­(OAc)₂), however, the desired hydroselenation of internal <i>N</i>-vinyl lactams proceeds efficiently to afford the corresponding <i>N</i>,<i>Se</i>-acetals

Can Wound Exudate from Venous Leg Ulcers Measure Wound Pain Status?: A Pilot Study

<div><p>We investigated the associations between the self-evaluated pain status and two pain biomarker candidates, nerve growth factor and S100A8/A9, in exudate from venous leg ulcer to finally develop an objective pain evaluation method. Patients with venous leg ulcer participated in this cross-sectional observational study conducted between April and October 2014 at two medical facilities. During routine wound care, each participant self-evaluated their pain status at each examination using the 10-point numerical rating scale (present pain intensity) and the short-form McGill Pain Questionnaire 2 (continuous pain, intermittent pain, neuropathic pain, affective descriptors, and total score). Venous leg ulcer exudate sample was collected after wound cleansing. The nerve growth factor and S100A8/A9 concentrations in the venous leg ulcer exudate were measured by enzyme-linked immunosorbent assay and standardized according to the wound area. The association between each pain status and the two standardized protein concentrations was evaluated using Spearman’s correlation coefficient. In 30 sample collected from 13 participants, the standardized nerve growth factor concentration was negatively correlated with continuous pain (<i>ρ</i> = -0.47, <i>P</i> = 0.01), intermittent pain (<i>ρ</i> = -0.48, <i>P</i> = 0.01), neuropathic pain (<i>ρ</i> = -0.51, <i>P</i> = 0.01), and total score (<i>ρ</i> = -0.46, <i>P</i> = 0.01). The standardized S100A8/A9 concentration was positively correlated with present pain intensity (<i>ρ</i> = 0.46, <i>P</i> = 0.03) and continuous pain (<i>ρ</i> = 0.48, <i>P</i> = 0.03). Thus, these two proteins may be useful for objective evaluation of wound pain in venous leg ulcer patients.</p></div