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Many hydrogen abstraction reactions on sp3 carbons with oxyradicals take place site-selectively (regioselectively). To investigate this selectivity, ab initio and density functional theory (DFT) calculations were carried out using cyclopentanone and SO4-˙ as the substrate and oxyradical, respectively. At the ωB97XD/6-311+G(d,p) level, the energy barriers for the forward process (ΔE1‡) of both α- and β-hydrogen abstraction were predicted to be 54.6 and 50.9 kJ mol-1, respectively. Consideration of solvent effects (acetonitrile) decreased these energy barriers to 33.2 and 26.1 kJ mol-1, respectively. These calculation outcomes suggested that β-hydrogen abstraction would be favourable, which supports experimental findings (i.e. β-selective abstraction). At the ωB97XD level, investigations into hydrogen abstraction from cyclohexanone with SO4-˙ confirmed the regioselectivity observed experimentally. Hydrogen abstractions from 2-propylpyridine and 3-methyl-1-butanol using SO4-˙, which are unknown reactions, were also calculated using the DFT method, and the predicted regioselectivity was consistent with that in the known reactions using tetrabutylammonium decatungstate (TBADT). In addition, regioselectivities in unexplored hydrogen abstractions of cyclopentanone by several oxyradicals were predicted. Natural bond orbital (NBO) analysis carried out at the ωB97XD level indicated that the transferred hydrogen atom is partially positively charged when abstracted by an oxyradical. Interestingly, hydrogens bonded to the most positively charged carbon in the substrate were predominantly abstracted by oxyradicals in practice, which should be a simple compass for predicting regioselectivity in the functionalisation of C(sp3)-H bonds with oxyradicals.

Glycogen debranching enzyme (GDE), together with glycogen phosphorylase (GP), is responsible for the complete degradation of glycogen. GDE has distinct catalytic sites for 4-α-glucanotransferase and amylo-α-1,6-glucosidase. For the GDE sensitive assay, we previously developed the GP limit fluorogenic branched dextrin Glcα1–4Glcα1–4Glcα1–4Glcα1–4(Glcα1–4Glcα1–4Glcα1–4Glcα1–6)Glcα1–4Glcα1–4Glcα1–4GlcPA (B4/84, where Glc = d-glucose and GlcPA = 1-deoxy-1-[(2-pyridyl)amino]-d-glucitol). However, B4/84 is not widely available because of difficulties in its chemical synthesis and positional-isomer separation (0.33% yield by α-1,6-coupling of maltotetraose with Glc7-GlcPA). In this study, we attempted to develop an efficient method for the preparation of Glcα1–4Glcα1–4Glcα1–4Glcα1–4(Glcα1–4Glcα1–4Glcα1–4Glcα1–6)Glcα1–4Glcα1–4GlcPA (B3/74), which was designed to have the minimum essential dextrin structure for GDE. First, Glcα1–6Glcα1–4Glcα1–4GlcPA (B3/31) was prepared from commercially available Glcα1–6Glcα1–4Glcα1–4Glc. Using α-cyclodextrin as a donor substrate, cyclodextrin glucanotransferase elongated both the main and side branches on B3/31, while all the glycosidic bonds in B3/31 were left intact. After exhaustive digestion with GP, B3/74 was obtained from B3/31 with 16% yield, a value that is 48-fold greater than that previously reported for B4/84. GDE 4-α-glucanotransferase exhibited high activity toward both B3/74 and B4/84. In addition, we studied the efficient conversion of B3/74 into Glcα1–4Glcα1–4Glcα1–4Glcα1–4(Glcα1–6)Glcα1–4Glcα1–4GlcPA (B3/71), which has the best dextrin structure for the GDE amylo-α-1,6-glucosidase.

Background Detailed histological evaluation is important in the diagnosis of autoimmune pancreatitis (AIP). However, it remains challenging to obtain adequate tissue from the pancreas. Recently, several reports have suggested the usefulness of endoscopic ultrasound-guided fine-needle biopsy (EUS-FNB) using the new “core” needles for acquiring pancreatic tissue. We aimed to investigate the usefulness of EUS-FNB for diagnosing AIP with one such needle, a 22-gauge Franseen needle. Methods Patients who met the imaging diagnostic criteria for AIP based on the International Consensus Diagnostic Criteria (ICDC) were enrolled in the study. All patients underwent EUS-FNB with a 22-gauge Franseen needle. Histological findings were evaluated based on the ICDC, and the detection rates of level 1 and level 1 or 2 histology were calculated. Results 56 patients from 11 different institutions were enrolled in the final analysis (55 suspected to have type 1 AIP and one with type 2 AIP). Lymphoplasmacytic infiltration, obliterative phlebitis, storiform fibrosis, and > 10 IgG4-positive cells per high-power field were detected in 55 (100 %), 24 (43.6 %), 40 (72.7 %), and 36 (65.5 %) of the 55 patients, respectively. The detection rates of level 1 and level 1 or 2 histology for AIP were 58.2 % (95 % confidence interval [CI] 44.1 % – 71.3 %) and 92.7 % (95 %CI 82.4 % – 98.0 %), respectively, which were apparently higher than our historical results (7.9 % [95 %CI 1.7 % – 21.4 %] and 62.2 % [95 %CI 46.5 % – 76.2 %], respectively) using a conventional needle. Conclusions EUS-FNB with a 22-gauge Franseen needle demonstrated favorable detection rates which would be clinically beneficial for the histological diagnosis of AIP.

The decyanation of secondary aliphatic nitriles and the 2-fold decyanation of malononitriles leading to alkanes in the presence of 1,3-dimethylimidazol-2-ylidene borane (diMeImd-BH3) are reported. ...

Glycogen debranching enzyme (GDE) is bifunctional in that it exhibits both 4-α-glucanotransferase and amylo-α-1,6-glucosidase activity at two distinct catalytic sites. GDE converts the phosphorylase-limit biantennary branch [G-G-G-G-(G-G-G-G↔)G-G- residue, where G = D-glucose, hyphens represent α-1,4-glycosidic bonds, and the double-headed arrow represents an α-1,6-glycosidic bond] into a linear maltooligosyl residue, which is then subjected to phosphorylase, and glycogen degradation continues. The prevailing hypothesis regarding the glycogen debranching pathway was that 4-α-glucanotransferase converts the phosphorylase-limit biantennary branch into the G-G-G-G-G-G-G-(G↔)G-G- residue and amylo-α-1,6-glucosidase cleaves the remaining α-1,6-linked G residue. In the present study, we analyzed the substrate specificities of 4-α-glucanotransferase and amylo-α-1,6-glucosidase using fluorogenic biantennary dextrins such as G-G-G-G-(G-G-G-G↔)G-G-GPA (F4/4/2; where GPA = 1-deoxy-1-[(2-pyridyl)amino]-D-glucitol), G-(G-G-G-G↔)G-G-GPA (F1/4/2), and G-G-G-G-G-G-G-(G↔)G-G-GPA (F7/1/2). Contrary to the prevailing hypothesis, the main branch of F4/4/2 was an important donor substrate component of 4-α-glucanotransferase and did not serve as an acceptor substrate. However, when G-G-G-G-G-GPA was added to the mixture, it successfully accepted a maltotriosyl (G

We searched for the $\alpha$ condensed state in $^{13}$C by measuring the $\alpha$ inelastic scattering at $E_{\alpha} = 388$ MeV at forward angles including 0 degrees. We performed the distorted-wave Born-approximation calculation with the single-folding potential and the multipole decomposition analysis to determine the isoscalar transition strengths in $^{13}$C. We found a bump structure around $E_x = 12.5$ MeV due to the isoscalar monopole ($IS0$) transition. A peak-fit analysis suggested that this bump consisted of several $1/2^-$ states. We propose that this bump is due to the mirror state of the 13.5 MeV-state in $^{13}$N, which dominantly decays to the $\alpha$ condensed state in $^{12}$C. It was speculated that the $1/2^-$ states around $E_x = 12.5$ MeV were candidates for the $\alpha$ condensed state, but the $3\alpha + n$ orthogonality condition model suggests that the $\alpha$ condensed state is unlikely to emerge as the negative parity states. We also found two $1/2^+$ or $3/2^+$ states at $E_x = 14.5$ and 16.1 MeV excited with the isoscalar dipole ($IS1$) strengths. We suggest that the 16.1-MeV state is a possible candidate for the $\alpha$ condensed state predicted by the cluster-model calculations on the basis of the good correspondence between the experimental and calculated level structures. However, the theoretical $IS1$ transition strength for this state is significantly smaller than the measured value. Further experimental information is strongly desired to establish the $\alpha$ condensed state in $^{13}$C., Comment: 24 pages, 12 figures, published in PTEP

Objectives: The time to recurrent biliary obstruction (TRBO) of unresectable distal malignant biliary obstruction is generally thought to be longer when a self‐expandable metal stent (SEMS) with a thicker inner diameter is used for drainage, but the dependence on the inner diameter using a fully covered SEMS (FCSEMS) is uncertain. The objective of this multicenter prospective study was to compare TRBO and adverse events, such as cholecystitis and pancreatitis, in treatment of patients with unresectable malignant biliary obstruction using 8‐ and 10‐mm diameter FCSEMS. Methods: Eighteen tertiary‐care centers participated in the study. Patients were allocated to the 8‐ and 10‐mm diameter groups. TRBO, non‐inferiority of the 8‐mm FCSEMS, overall survival time, frequency and type of adverse events, and non‐recurrent biliary obstruction (RBO) rate at the time of death were compared between the two groups. Results: Median TRBO did not differ significantly between the 8‐mm (n = 102) and 10‐mm (n = 100) groups (275 vs 293 days, P = 0.971). The hazard ratio of the 8‐ to 10‐mm groups was 0.90 (80% confidence interval, 0.77–1.04; upper limit lower than the acceptable hazard ratio [1.33] of the null hypothesis). Based on these findings, the 8‐mm diameter stent was determined to be non‐inferior to the 10‐mm diameter stent. Survival time, incidence of adverse events and non‐RBO rate at the time of death did not differ significantly between the two groups. Conclusions: Time to RBO with an 8‐mm diameter FCSEMS was non‐inferior to that with a 10‐mm diameter FCSEMS. This finding is important for development of future SEMS., ファイル公開：2020-07-01

We report the regioselective trifluoromethylation of 1,3-bis(vinyl triflates) via an allyl radical intermediate. In this reaction, the trifluoromethyl radical exclusively attacks the 4-position of the 1,3-diketone derivatives. The observed regioselectivity can be rationalized on the basis of DFT calculations, which suggest that the attack at the 4-position is more favorable than that at the 2-position. We have also developed a one-pot procedure for the regioselective trifluoromethylation of 1,3-diketones.

Bromination is an important transformation in organic synthesis, and novel efficient bromination techniques are still required. Herein, we demonstrate atom-economical brominations using (DMI)2HBr3, a novel tribromide complex, with oxidants such as DMSO and Oxone. Using this system, olefinic and aromatic brominations, as well as selective α-monobrominations of ketones proceeded well to afford the desired bromides in good yields. Importantly, in these reactions all of the bromine atoms in this complex are used to brominate.

We herein report a case of a 75-year-old woman who presented with a low-grade fever, repeated cold-induced urticaria, and painful leg edemas with neutrocytosis. Because her mother also had cold-induced urticaria and her skin lesions histologically showed neutrophilic dermatitis, we suspected that she had familial cold autoinflammatory syndrome, a subtype of cryopyrin-associated periodic syndromes. Sequencing of the NLRP3 and MEFV genes revealed that she carried both the p.A439V missense mutation and p.E148Q homozygous mutation, which is commonly detected in familial Mediterranean fever patients. The administration of colchicine reduced the frequency and severity of her skin rash and leg edema.

Although molecular bromine (Br2) is a useful brominating reagent, it is not easy to handle. Herein, we describe the preparation of a novel air-stable bromine complex prepared from 1,3-dimethyl-2-imidazolidinone (DMI) and Br2, which was identified to be (DMI)2HBr3 by spectral and X-ray techniques. This complex was then used to brominate olefins, carbonyl compounds, and aromatics, as well as in the Hofmann rearrangement. Yields of reaction products using this complex were almost the same or superior to those using other bromine alternatives.

Although carbon monoxide (CO) is considered a practical source of the carbonyl functionality in various compounds, handling CO gas is difficult. The phase-vanishing (PV) method, using highly fluorinated solvents as the phase screen, was thus employed, in which CO was evolved for use in organic synthesis. An H-shaped reactor bearing two reaction chambers was employed. In the first chamber, CO was efficiently generated from sulfuric acid and ammonium formate under the PV conditions, and then consumed in the second chamber in a range of palladium-catalysed carbonylation reactions, affording the desired products. Use of this PV system allowed for easy and safe generation of hazardous CO gas, and its use thereof in organic synthesis.

Objective: To evaluate the efficacy and safety of alternate-day administration of S-1 as second-line chemotherapy for unresectable pancreatic cancer in a multicenter, randomized, phase II study. Methods: Patients with histologically proven, unresectable pancreatic cancer treated with chemotherapy not including S-1 as first-line therapy were randomly assigned to receive either daily or alternate-day treatment with S-1. The primary end point was overall survival (OS), and the secondary end points were progression-free survival (PFS), time to treatment failure (TTF), response rate, and adverse events. Results: A total of 77 patients were enrolled, of which 75 were included in the final analysis. The median OS was 4.5 months in the daily group and 4.4 months in the alternate-day group (HR 1.178; 95% CI 0.741–1.875), with no significance in PFS and TTF. The response rate was 2.8% in the daily group and 0% in the alternate-day group. Grade 3 or higher adverse events occurred with significantly higher incidence in the daily group (47.2 vs. 25.6%, p = 0.044). Conclusion: As a second-line chemotherapy for unresectable pancreatic cancer, although the efficacy in both groups was comparable and we can expect fewer toxicities with alternate-day administration of S-1, the noninferiority of alternate-day treatment to daily treatment with S-1 was not verified.

The redox-neutral tetrafluoroethylation of alkynes with 1,1,2,2-tetrafluroroethanesulfonic acid (TFESA) and azobis(isobutyronitrile) (AIBN) proceeds via the formation of vinyl tetrafluoroethanesulfonates followed by a radical tetrafluoroethylation. Experimental and theoretical results support an intermolecular reaction.

The structure of a neutron-rich ^{25}F nucleus is investigated by a quasifree (p,2p) knockout reaction at 270A MeV in inverse kinematics. The sum of spectroscopic factors of π0d_{5/2} orbital is found to be 1.0±0.3. However, the spectroscopic factor with residual ^{24}O nucleus being in the ground state is found to be only 0.36±0.13, while those in the excited state is 0.65±0.25. The result shows that the ^{24}O core of ^{25}F nucleus significantly differs from a free ^{24}O nucleus, and the core consists of ∼35% ^{24}O_{g.s.}. and ∼65% excited ^{24}O. The result may infer that the addition of the 0d_{5/2} proton considerably changes neutron structure in ^{25}F from that in ^{24}O, which could be a possible mechanism responsible for the oxygen dripline anomaly.

The decyanation of secondary aliphatic nitriles and the 2-fold decyanation of malononitriles leading to alkanes in the presence of 1,3-dimethylimidazol-2-ylidene borane (diMeImd-BH

An ion trap/time-of-flight mass spectrometer equipped with a metastable atom bombardment (MAB) ionization source was constructed in order to observe ion-molecule reactions controlled by the internal energy of ions. In the MAB source, the internal energy of the generated ions was controlled by using different rare gases. Moreover, the constructed device was used to analyze ion-molecule reactions of the p-xylene cation and its dissociation ions with p-xylene. It was found that the reaction afforded a single product without any structural isomers, which could then be easily analyzed. An abundant amount of [M]+ (m/z 106, C8H10+ ) and trace levels of dissociation products were observed in the Kr MAB ionization, while in the Ar MAB ionization, [M−CH3]+, [M−H]+ (m/z 105, C8H9+), and [M+CH]+ (m/z 119, C9H11+) ions were generated in addition to the molecular ion. Moreover, investigating the production routes to [M−H]+ and [M+CH]+ ions using a resonance ejection method in the ion trap indicating that generation of these ions was related to the hydride transfer reaction of C7H7+ with p-xylene. Results from the calculations of the reaction profile of this transfer using the density functional theory (DFT) method supported the experimental results.

Trifluoromethylation using Umemoto's reagent is an important transformation that allows the preparation of compounds bearing trifluoromethyl groups. To investigate the mechanism of this reaction, ab initio and density functional theory (DFT) calculations were carried out using pyrrole, aniline, sodium acetylacetonate, and sodium methyl acetoacetate as nucleophiles. At the highest level of theory examined (i.e., CCSD(T)/6-311+G(d,p)//M06-2X/6-311+G(d,p)), the energy barriers for the forward process (ΔE‡1) of both the backside and frontside attack of pyrrole on a model Umemoto reagent (i.e., S-(trifluoromethyl)dimethylsulfonium, CF3DMS) were predicted to be 135.9 and 192.3 kJ mol-1, respectively, while values of 131.9 and 188.2 kJ mol-1 were obtained at the MP2/6-311+G(d,p)//M06-2X/6-31+G(d,p) level. These outcomes suggest that the reaction proceeds via the backside mechanism. Using the MP2 method, the investigation of the trifluoromethylation of pyrrole and sodium acetoacetate with the sulfonium moiety of Umemoto's reagent, S-(trifluoromethyl)dibenzothionium, revealed that this reaction would also occur through the backside mechanism, thereby indicating that this pathway remains feasible despite solvent effects. Finally, computational investigations revealed that the simple single-electron transfer mechanism, which should occur between Umemoto's reagent and nucleophiles, did not take place during this reaction.

Although borane is a useful reagent, it is difficult to handle. In this study, borane was generated in situ from NaBH4 or nBu4NBH4 with several oxidants using a phase-vanishing (PV) method. The borane generated was directly reacted with alkenes, affording the desired alcohols in good yields after oxidation with H2O2 under basic conditions. The selective reduction of carboxylic acids with the evolved borane was examined. The organoboranes generated by the PV method successfully underwent Suzuki–Miyaura coupling. Using this PV system, reactions with borane can be carried out easily and safely in a common test tube.

The phase-vanishing (PV) method using perfluorohexanes as the phase screen was applied to the aldol condensation using TiCl 4 as the Lewis acid. A special test tube was used, in which an interface between the fluorous and organic layers was stirred, and cyclohexanone was treated with two equivalents of benzaldehyde derivatives under PV conditions to afford corresponding 2,6-dibenzylidencyclohexanone in good yields. The formyl-methylenation of ketones with triethylamine using TiCl 4 was also demonstrated by the PV method.

A solution of hydrogen bromide (HBr) in 1,4-dioxane was prepared and investigated for its ability to brominate alcohols, and hydrobrominate alkenes. This study revealed that the brominating ability of this HBr/1,4-dioxane solution is equal or superior to that of hydrobromic acid or HBr in acetic acid. The solution of HBr in 1,4-dioxane is robust, exhibiting no decomposition of the solvent, and retaining 97% of its original concentration, when kept at −25 °C for 30 days. This solution is a liquid alternative to HBr gas without protic solvents.

This paper presents boundary conditions for lateral buckling of the H-shaped beams connected to columns by flush end plates which fall into the lateral buckling following the out of plane plastic deformations of the flush end plates. The study is conducted by the following procedure: First, the behavior of the connection is researched by the no buckling experiment under the cyclic loading. As a result, it is found that the relationship between the out of plane plastic deformations of the endplates and the bending moment at the beam end can be predicted. Next, the FEM analyses of the rigid-frame structures consist of the slender beams having flush end plates connection and the structures consist of the beams having rigid connection are conducted to research the stress conditions in the tension flanges and the compression flanges of the beams during falling into lateral buckling. As a result, it is found that the rigid connection is restraining warping of the beam more tightly than the flush end plates connection, then the maximum bending moment strength against lateral buckling of the beams connected by rigid connections is higher than those of the beams connected by flush endplate. We recommend that the boundary conditions for the lateral buckling of the beams connected by flush end plates should be regarded to be different from those of the beams connected by the rigid connections.

DFT calculations were carried out to elucidate the 1,4-hydrogen shift of 1-hydroxyallyl radicals to give α-keto radicals. The 1,4-H shift is predicted to be exothermic with large energy barriers. H...

Aminocarbonylation of aromatic iodides with CO and amines gives aromatic amides under photoirradiation conditions. DFT calculations predict that methylamine adds to benzoyl radical to give a zwitte...

A woman in her 70s presented to our hospital with epigastric pain, back pain, and weight loss. Esophagogastroduodenoscopy was performed, and numerous protuberances, which were suspected to be submucosal tumors, were found at the gastric corpus. The patient was diagnosed with gastric tuberculosis based on the biopsy results of these protuberances. Histopathological analysis demonstrated non-caseating epithelioid granuloma. A positive culture for Mycobacterium tuberculosis was also obtained on gastric juice analysis and confirmed using polymerase chain reaction assay. In the rapidly aging population in Japan, our findings emphasize on the importance of differentiating gastrointestinal tuberculosis, including gastric tuberculosis, from other diseases. This case may provide information about the development of gastric tuberculosis.

The base-free palladium-catalyzed borylation of aryl chlorides with diborons was achieved. The base-free conditions offered acceptable functional group compatibility. Based on experimental and computational studies, it was shown that smooth boryl transfer from the diborons to the arylpalladium chloride was promoted by strong interaction between the Lewis acidic boron and the chlorine atom on palladium.

Fluorous Yamaguchi (FY) reagents bearing a perfluoroalkyl chain were prepared and employed in esterification reactions; the yields were similar to those obtained with the traditional Yamaguchi (TY) reagent. Fluorous benzoic acids derived from the FY reagents were separated easily after the reaction. GC analysis revealed that the initial rates of reaction with the FY reagents were higher than those with the TY reagent. The acidities of benzoic acids produced from the FY and TY reagents were predicted by DFT to be similar (1.20 and 0.96, respectively).

Using a phase-vanishing (PV) system, hydrogen, oxygen, and hydrogen sulfide generated in situ from CaH2, KO2, and P2S5, respectively, were directly reacted with substances in the organic phase to afford the desired products. The selective synthesis of sulfides and disulfides was achieved with the evolution of H2S gas via tuning the bases used in the PV method. Using this PV system, reactions with hazardous gaseous reagents can be carried out easily and safely in a common test tube.

Vinyl ethers are important and useful synthetic building blocks. Using a test tube with a screw cap, a convenient preparation of vinyl ethers from alcohols with calcium carbide under superbasic catalytic conditions (KOH/DMSO) was developed. The vinylation of primary and secondary alcohols was successfully achieved, affording the desired products in good yields. The gram-scale preparation of a vinyl ether was also demonstrated. In this reaction, calcium carbide acts as an acetylene source, constituting a safer alternative to acetylene gas.

Rechargeable batteries using organic cathode materials are expected to afford high mass energy densities since these materials can undergo multiple electron redox reactions per molecule. Although the batteries using benzoquinone (BQ) derivatives as organic cathode active materials exhibited high theoretical capacity, their practical capacities and cycle retention were far from satisfactory. To overcome these problems, dimeric BQ derivatives based on the 2,2′-bis-p-benzoquinone (BBQ) framework were synthesized, and the charge–discharge behaviour of the prepared cells using BBQs as the cathode active materials was investigated. BBQ-based cells exhibited excellent performance compared to those based on BQ monomers. For example, the BBQ cell afforded a high initial capacity of 358 A h kg−1 (more than twice that of current lithium-ion batteries that use LiCoO2 as the cathode active material) and a high cycle retention of 198 A h kg−1 at 50 cycles. Electrochemical measurements and density functional theory (DFT) calculations indicated that three electron-redox reactions generally occur in BBQ derivatives, although (OMe)2-BBQ appeared to undergo a four-electron redox reaction.

1,4-Hydrogen transfer from the 1-hydroxyallyl radical to give the enoxyl (α-keto) radical is an exothermic process with a high activation energy based on DFT calculations. The lack of experimental examples of such 1,4-H shift reactions lies in the difficulty of generating the 1-hydroxyallyl radical. We have shown that radical carbonylation of alkenyl radicals with CO followed by nucleophilic trapping of the carbonyl portion of the resulting radical by amines gives rise to 1-amino-substituted 1-hydroxyallyl radicals in situ. At the outset of this chemistry, we examined intramolecular trapping reactions via radical carbonylation of alkynylamines mediated by tributyltin hydride. Consequently, α-methylene lactams were obtained, for which the initially formed 1-amino-substituted 1-hydroxyallyl radical underwent a 1,4-H shift followed by subsequent β-scission, which led to the expulsion of a tributyltin radical. A competing pathway of the 1,4-H shift of 1-amino-substituted 1-hydroxyallyl radicals involving hydrogen abstraction was observed, which led to the formation of α-stannylmethylene lactams as a major byproduct. However, in contrast, when intermolecular trapping of α-ketenyl radicals by amines was carried out, the 1,4-H shift from the 1-amino-substituted 1-hydroxyallyl radical became the major pathway, which gave good yields of α,β-unsaturated amides. Thus, we were able to develop three-component reactions comprising terminal alkynes, CO, and amines that led to α,β-unsaturated amides via the 1,4-H shift reaction. DFT calculations support the observation that the 1,4-H shift is more facile when 1-hydroxyallyl radicals have both 1-amino and 3-tin substituents. The choice of substituents on the amine nitrogen is also important, since N-C bond cleavage via an S

The Tokyo metropolitan area is the largest world city-region globally, and is the location where many of Japan’s advanced functions are centralized. The competitive power of new cultural industries has been demonstrated in recent years. To enhance creativity and strengthen the international competitiveness of cultural industries, it is important to convert the internal structure of Tokyo’s urban areas and to accelerate connections among various industrial agglomerations in the metropolitan area.