Direct synthesis of phenanthrenyl triflates from 1-biphenylyl-2-diazo-2-aryl ketones and triflic anhydride.

A strategy for direct synthesis of phenanthrenyl triflates from 1-biphenylyl-2-diazo-2-aryl ketones and triflic anhydride is described. The reaction of 1-biphenylyl-2-diazo-2-aryl ketones with triflic anhydride proceeded smoothly in the presence of 2,6-di-tert-butylpyridine under mild conditions to produce phenanthrenyl triflates in high to excellent yields. The phenanthrenyl triflate products were demonstrated to be utilized as coupling partners in various coupling reactions. The proposed mechanism involves an intramolecular Friedel-Crafts reaction of a vinyl cation intermediate formed in situ.

The effect of preoperative rehabilitation on the prevention of postoperative ileus in colorectal cancer patients.

PURPOSE: Previous research suggests that the preoperative rehabilitation of colorectal cancer patients can reduce postoperative ileus. However, the evidence is insufficient and further research is warranted. This study aimed to investigate whether short-term preoperative rehabilitation, both on an outpatient and inpatient basis, can reduce the incidence of postoperative ileus after colorectal cancer surgery. METHODS: This was a retrospective cohort study that drew on data from multicenter electronic medical records. Patients with stage 1-3 colorectal cancer who underwent surgery and postoperative rehabilitation were included. The incidence of postoperative ileus was compared between patients who received short-term preoperative rehabilitation and those who did not. Propensity score adjustment using inverse probability weighting and subgroup analysis by type of surgery was performed. RESULTS: Four thousand seventy-six eligible patients (43.4% female; mean age 75.1 ± 10.9 years) were included; 1914 (47.0%) received short-term preoperative rehabilitation. The preoperative rehabilitation group had a significantly lower incidence of postoperative ileus than the no preoperative rehabilitation group (pre-adjustment: 5.5% vs. 9.9%, p < 0.001; post-adjustment: 5.2% vs. 9.0%, p < 0.001). Therefore, preoperative rehabilitation was significantly associated with a lower incidence of postoperative ileus (OR: 0.554, 95% CI: 0.415-0.739, p < 0.001). In an adjusted analysis of surgery type subgroups, the incidence of postoperative ileus was significantly lower in the preoperative rehabilitation group for all types of surgery. CONCLUSION: Our study showed that short-term preoperative rehabilitation for patients with stage 1-3 colorectal cancer, both with inpatients and outpatients, significantly reduces the incidence of postoperative ileus.

Influence of Chewing Gummy Jelly Containing Aroma Compound on Psychological Stress and Autonomic Nervous System Activity: A Randomized Crossover Trial.

The aim of this randomized crossover trial was to clarify the effects of chewing gummy jelly containing a compound of decanoic acid, oligonol, methyl cellulose, and citral (DOMAC) on mental stress and autonomic nervous activity in facemask wearers. A placebo gummy jelly was used in conjunction with DOMAC. Eight healthy adults with no tooth loss (mean age: 35±5 yr) were included. The participants were required to chew one DOMAC or placebo gummy jelly for 5 min after wearing a facemask for 20 min in the laboratory, then the other gummy jelly after a washout period. Rate of change in salivary immunoglobulin A (IgA) as a marker of stress was compared between before and after chewing. Additionally, sympathetic and parasympathetic activity was compared at both time points. A significant difference was observed in the percentage change in salivary IgA from that at before wearing a facemask: 127±34% (mean±standard deviation) while wearing a facemask; 46±20% while chewing DOMAC gummies; and 47±26% while chewing placebo gummies (p<0.05). Parasympathetic nervous system activity was 971.2±1040.7 ms2 at 20 min after facemask wearing; 295.0±253.0 ms2 after DOMAC gummy chewing; and 1956.1±2798.0 ms2 after chewing a placebo gummy jelly; with significant differences only being found between 20 min after facemask wearing and after DOMAC gummy chewing (p<0.05). Sympathetic nervous system activity was 1.80±1.83 at 20 min after facemask wearing; 4.06±3.33 after DOMAC gummy chewing; and 4.95±7.02 after chewing a placebo gummy jelly; with significant differences only being found between 20 min after facemask wearing and after DOMAC gummy chewing. These results suggest that chewing gummy jellies containing DOMAC relieves stress caused by facemask wearing and activates sympathetic nervous system activity.

Palladium-Catalyzed Tail-to-Tail Reductive Dimerization of Terminal Alkynes to 2,3-Dibranched Butadienes.

The palladium-catalyzed tail-to-tail reductive dimerization of terminal alkynes is described for the first time. Aromatic terminal alkynes bearing diverse and sensitive functional groups as well as aliphatic terminal alkynes are efficiently transformed to 2,3-dibranched butadienes. The key to achieve a selective tail-to-tail reductive dimerization reaction is to control appropriately the acidity of the reaction solution, which is accomplished by a combined use of pivalic acid and para-toluenesulfonic acid. The tail-to-tail reductive dimerization reaction is proposed to proceed via a cationic alkenyl palladium intermediate under acidic conditions.

Chiral Indolizidine Synthesis through the Ir-Catalyzed Asymmetric Hydrogenation of Cyclic Pyridinium Salts.

The Ir-catalyzed asymmetric hydrogenation of cyclic pyridinium salts is presented as a new strategy for the convenient and efficient synthesis of chiral indolizidines. The asymmetric hydrogenation of cyclic pyridinium salts derived from 2-(2-acylphenyl)pyridines proceeded smoothly in the presence of [Ir(cod)Cl]2 and (R)-DM-SegPhos to provide the desired chiral 7,8-benzoindolizidines 6 in high to excellent yields with moderate enantioselectivity (up to 86:14 er) and excellent diastereoselectivity (>20:1 dr). The enantiomeric purity of 6j was increased to 92:8 through recrystallization.

Interweaving Visible-Light and Iron Catalysis for Nitrene Formation and Transformation with Dioxazolones.

Herein, visible-light-driven iron-catalyzed nitrene transfer reactions with dioxazolones for intermolecular C(sp3 )-N, N=S, and N=P bond formation are described. These reactions occur with exogenous-ligand-free process and feature satisfactory to excellent yields (up to 99 %), an ample substrate scope (109 examples) under mild reaction conditions. In contrast to intramolecular C-H amidations strategies, an intermolecular regioselective C-H amidation via visible-light-induced nitrene transfer reactions is devised. Mechanistic studies indicate that the reaction proceeds via a radical pathway. Computational studies show that the decarboxylation of dioxazolone depends on the conversion of ground sextet state dioxazolone-bounding iron species to quartet spin state via visible-light irradiation.

Synthesis of 1H-Indole-2,3-dicarboxylates via Rhodium-Catalyzed C-H Annulation of Arylhydrazines with Maleates.

This work describes a one-step synthesis of 1H-indole-2,3-dicarboxylates through C-H activation. Rhodium-catalyzed tandem C-H activation and annulation of 2-acetyl-1-phenylhydrazines with maleates proceeded smoothly in the presence of additive NaOAc and oxidant Ag2CO3 and produced the corresponding indole derivatives, 1H-indole-2,3-dicarboxylates, in satisfactory to good yields. A variety of useful functional groups were tolerated on the benzene ring including halogen atoms (F, Cl, Br, and I) and methoxycarbonyl groups.

Copper-Catalyzed One-Pot Synthesis of 1,3-Enynes from 2-Chloro-N-(quinolin-8-yl)acetamides and Terminal Alkynes.

A method for the chemo-, regio-, and stereoselective one-pot synthesis of 1,3-enynes is described. The reaction of 2-chloro-N-(quinolin-8-yl)acetamides with terminal alkynes proceeds smoothly in the presence of a copper catalyst at room temperature to produce (E)-1,3-enynes in satisfactory to excellent yields. The mechanism study reveals that the cross-dimerization of internal alkynes generated in situ with terminal alkynes proceeds via allene intermediates. The directing group 8-aminoquinoline plays a key role in the current selective synthesis of (E)-1,3-enynes.

Structural Study on Fat Crystallization Process Heterogeneously Induced by Graphite Surfaces.

Some inorganic and organic crystals have been recently found to promote fat crystallization in thermodynamically stable polymorphs, though they lack long hydrocarbon chains. The novel promoters are talc, carbon nanotube, graphite, theobromine, ellagic acid dihydrate, and terephthalic acid, among which graphite surpasses the others in the promotion effect. To elucidate the mechanism, we investigated the influence of graphite surfaces on the crystallization manner of trilaurin in terms of crystal morphology, molecular orientation, and crystallographic features. Polarized optical microscopy, cryo-scanning electron microscopy, synchrotron X-ray diffractometry, and polarized Fourier-transform infrared spectroscopy combined with the attenuated total reflection sampling method were employed for the analyses. All the results suggested that the carbon hexagonal network plane of graphite surfaces have a high potential to facilitate the clustering of fat molecules against high thermal fluctuations in fat melt, the fat molecules form a layer structure parallel to the graphite surface, and the clusters tend to grow into thin plate crystals of the ß phase at the temperatures corresponding to low supercooling. The ß' phase also has a larger chance to grow on the graphite surface as supercooling increases.

Binary Phase Behavior of 1,3-Distearoyl-2-oleoyl-sn-glycerol (SOS) and Trilaurin (LLL).

This paper reports the precise analysis of the eutectic mixing behavior of 1,3-distearoyl-2-oleoyl-sn-glycerol (SOS) and trilaurin (LLL), as a typical model case of the mixture of cocoa butter (CB) and cocoa butter substitute (CBS). SOS was mixed with LLL at several mass fractions of LLL (wLLL); the mixtures obtained were analyzed for polymorphic phase behavior using differential scanning calorimetry (DSC) and synchrotron radiation X-ray diffractometry (SR-XRD). In melt crystallization with constant-rate cooling, SOS and LLL formed eutectics in their metastable polymorphs, allowing the occurrence of a compatible solid solution at wLLL ≥ 0.925. With subsequent heating, the resultant crystals transformed toward more stable polymorphs, then melted in a eutectic manner. For mixtures aged at 25 °C after melt crystallization, eutectics were found in the extended wLLL region, even at wLLL = 0.975. These results indicate that phase separation between SOS and LLL progressed in their solid solution under stabilization. The crystal growth of the separated SOS fraction may cause fat-bloom formation in compound chocolate containing CB and CBS. To solve this problem, the development of retardation techniques against phase separation is expected.

Direct Carbohydroxylation of Arylalkenes with Allylic Alcohols: Cooperative Catalysis of Copper, Silver, and a Brønsted Acid.

The cooperative catalysis of copper, silver, and Brønsted acid is presented as a new strategy for olefin functionalization. The catalytic direct carbohydroxylation of arylalkenes with allylic alcohols provided a straightforward and efficient approach for preparing 4,5-unsaturated alcohols. Synthetically useful functional groups, such as Cl, Br, carbonyl, and chloromethyl, remained intact during the functionalization reaction.

Feedback protocol of 'fading knowledge of results' is effective for prolonging motor learning retention.

[Purpose] "Knowledge of results" (KR) is information about the success of an action relative to a goal. A reduced frequency of "knowledge of results" reportedly promotes motor learning more than a high frequency. However, the effect of gradually diminishing or increasing "knowledge of results" pattern has been rarely studied and is controversial. We investigated the effectiveness of diminishing "knowledge of results" pattern in motor learning. [Participants and Methods] Forty-six healthy adults were randomly assigned to either the 100% KR, 50% KR, or faded KR group. Participants were tasked with exerting 60% of their maximum voluntary contraction of their left shoulder flexion muscle in an isometric exercise. Participants practiced the task 20 times a day for 4 days. A pretest and posttest were conducted before and immediately after the acquisition, respectively. Retention tests were conducted 1 day, 1 week, and 2 weeks after the acquisition. [Results] The absolute error was significantly reduced in the posttest in the faded KR and 50% KR cohorts. However, there was no significant difference in the 100% KR group. In the faded KR subjects, the improvement effect was observed up to 1 week following acquisition. [Conclusion] Faded "knowledge of results" productively prolongs the effect of motor learning.

Pd-Catalyzed Consecutive C-H-Arylation-Triggered Cyclotrimerization: Synthesis of Star-Shaped Benzotristhiazoles and Benzotrisoxazoles.

Star-shaped π-extended molecules comprising discotic aromatic cores and peripheral π-conjugated arms have attracted significant attention as diverse optoelectronic materials in terms of their large π-surface, tunable self-assembly, enhanced charge transport and fluorescence, and liquid crystallinity. Although many efforts have been made in the construction of various aromatic discotic cores, a new class of C3 -symmetric star-shaped discotic π-molecules consisting of electron-deficient benzotristhiazole and benzotrisoxazole cores, which are expected to exhibit distinct optoelectronic properties, remains unexplored owing to the unachievable synthetic approaches involved in their synthesis. Herein, we report a novel and highly efficient Pd-catalyzed cyclotrimerization of the functionalized thiazoles or oxazoles for the construction of a new class of discotic molecules of benzotristhiazole and benzotrisoxazole central cores with star-shaped π-conjugated arms. The combination of [Pd2 (dba)3 ]/XPhos (dba=dibenzylideneacetone) catalyst systems with the 4-bromo-substituted thiazole enables the formation of a sufficiently stable thiazole-Pd species that participates in the subsequent C-H arylations consecutively to form the corresponding cyclic trimer products. This new class of star-shaped discotic π-extended products showed tunable energy levels and high fluorescence quantum yields that make them promising candidates for optoelectronic applications.

Palladium-Catalyzed Ligand-Controlled Regioselective Nucleophilic Aromatic Substitution of 1-(Chloromethyl)naphthalenes with Arylacetonitriles.

The palladium-catalyzed reaction of 1-(chloromethyl)naphthalenes 1 with (hetero)arylacetonitriles 2 gives either para- or ortho-acylated naphthalenes (3 or 4) in good to high yields. The regioselectivity can be controlled by the ligand of a palladium catalyst. A sterically bulky ligand, tBuPPh2, affords para-acylated products 3, whereas a sterically less bulky ligand, Me2PPh, provides ortho-acylated products 4. Further, direct substitution product 5 at the benzylic position is not obtained essentially, although such a reaction at the benzylic position is favorable in ordinary nucleophilic substitutions. In this paper, it was revealed that the benzylpalladium intermediate could react through a different mode (η3-benzylpalladium intermediate or η1-benzylpalladium intermediate) in nucleophilic aromatic substitution. In addition to the interesting mechanistic aspect, the present reaction provides a facile synthetic method for a wide range of diaryl ketones, some of which are not easily available through the previously known procedures.

Synthesis of Quinazolin-4(3 H)-ones via the Reaction of 2-Halobenzamides with Nitriles.

This paper describes a convenient method to synthesize quinazolin-4(3 H)-ones from simple and readily available 2-halobenzamides and nitriles. The Lewis acid Cu-catalyzed nucleophilic addition of 2-halobenzamide to nitriles followed by SNAr reaction proceeds smoothly in the presence of tBuOK as a base to produce quinazolinone derivatives.

Pd-Catalyzed cascade cyclization of o-alkynylanilines via C-H/C-N bond cleavage leading to dibenzo[a,c]carbazoles.

A new and efficient Pd-catalyzed cascade cyclization of biaryl-tethered o-alkynylanilines for the formation of dibenzo[a,c]carbazole derivatives has been reported. The use of the alkyl-substituted tertiary anilines together with the combination of the PdCl2 catalyst with the MnO2 oxidant and PivOH is vital for giving rise to 5-endo cyclization, C-N bond cleavage, and C-H bond activation in a cascade manner to produce the corresponding products with structural diversity.

Optimal fiber design for large capacity long haul coherent transmission [Invited].

Fiber figure of merit (FOM), derived from the GN-model theory and validated by several experiments, can predict improvement in OSNR or transmission distance using advanced fibers. We review the FOM theory and present design results of optimal fiber for large capacity long haul transmission, showing variation in design results according to system configuration.

Palladium-Catalyzed sp2-sp3 Coupling of Chloromethylarenes with Allyltrimethoxysilane: Synthesis of Allyl Arenes.

Palladium-catalyzed remote sp2-sp3 coupling reaction of chloromethylarenes with allyltrimethoxysilane is described in this work. The allylation reaction regioselectively occurred on the para-positions of 1-(chloromethyl)naphthalenes and benzyl chlorides to form new C(sp2)-C(sp3) bonds. The reaction proceeds smoothly under mild conditions to produce allyl arenes in moderate to excellent yields.

Synthesis of 5H-Dibenzo[c,e]azepine-5,7(6H)-diones from Benzamides via Palladium-Catalyzed Double C-H Bond Activation.

A convenient and efficient method for the synthesis of 5H-dibenzo[c,e]azepine-5,7(6H)-diones from simple and readily available benzamides is described in this work. The palladium-catalyzed homocoupling of benzamides occurred via ortho-selective double C-H bond activation using the simplest amide CONH2 as a directing group. The subsequent intramolecular condensation reaction proceeded smoothly to produce 5H-dibenzo[c,e]azepine-5,7(6H)-diones in satisfactory to excellent yields in one pot.

A study of synthetic approaches to 2-acyl DHA lysophosphatidic acid.

Lysophosphatidic acid (LPA) is a chemical mediator with a very simple glycerophospholipid structure. 1-Acyl LPA and 2-acyl LPA are biosynthesized in vivo. Unlike 1-acyl LPA, the biological function of 2-acyl LPA has been hardly elucidated and even organic synthesis of 2-acyl LPA had not been established. We suppressed acyl migration by formation of a salt with a phosphate group in order to synthesize 2-acyl LPA condensed with docosahexaenoic acid.