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We have developed a one-iridium-catalyst system that transforms

Ti–Pd alloys have been found to be novel heterogeneous palladium catalysts for organic cross-coupling reactions. Catalyst preactivation is not necessary, resulting in facile recovery and reuse of t...

N,N-Dimethylformamide-stabilised Pd nanocluster (NC) catalysed cross-coupling reactions of hydrosilane/disilane have been investigated. In this reaction, the coupling reaction proceeds without ligands with low catalyst loading. N,N-Dimethylacetamide is a crucial solvent in these reactions. The solvent effect was considered by various techniques, such as transmission electron microscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis. The Pd NCs can be recycled five times under both hydrosilane and disilane reaction conditions.

Oxido-alcoholato- and oxido-thiolato-molybdenum(VI) complexes bearing two ene-1,2-dithiolate ligands (cyclohexene-1,2-dithiolate) are prepared as synthetic models of molybdenum(VI) reaction centers of dimethyl sulfoxide reductase family of molybdenum enzymes. These complexes are prepared by oxygen atom transfer from tertiary amine N-oxide (trimethylamine N-oxide and N,N-dimethylaniline N-oxide) to the five-coordinate alcoholato- and thiolato-molybdenum(IV) complexes, and are characterized by UV–vis, cold-spray-ionization mass, resonance Raman, and 1H NMR spectroscopies. The oxygen atom transfer reactions are studied kinetically at a low temperature (−40 °C) to demonstrate that the reactivity of the thiolato-molybdenum(IV) complex is higher than that of alcoholato-molybdenum(IV) complex by about 7 times, and that the oxygen atom transfer reactivity increases with increasing the electron withdrawing ability of the p-substituent of N,N-dimethylaniline N-oxide derivatives. Mechanistic details are discussed based on the reactivity studies.

A nanoparticle (NP)-based precatalyst has been developed for organic synthesis: sulfur-modified Au-supported Fe (SAFe). The SAFe was easily prepared through a three-step procedure involving simultaneous in situ metal NP and nanospace organization (PSSO). This method avoids the need for preformed templates for immobilizing and stabilizing the metal nanoparticles. On account of the relative safety and enormous earth abundance of iron, SAFe potentially represents an ideal precatalyst for carbon–carbon bond-forming cross-coupling reactions. As such, it has been applied as a precatalyst to Kumada coupling under ligand-free conditions, proving to be capable of being recycled and used repeatedly for this reaction. Analysis of SAFe and of reaction mixtures suggested that the active species in these reactions are produced in situ by assemblies of iron-based NPs.

A simple method for the cross β-alkylation of linear alcohols with benzyl alcohols in the presence of DMF-stabilized iridium nanoparticles was developed. The nanoparticles were prepared in one-step and thoroughly characterized. Furthermore, the optimum reaction conditions have a wide substrate scope and excellent product selectivity.

Self-assembled multilayer iron(0) nanoparticles (NPs, 6-10 nm), namely, sulfur-modified Au-supported Fe(0) [SAFe(0)], were developed for ligand-free one-pot carbon-carbon/carbon-nitrogen bond-forming reactions. SAFe(0) was successfully prepared using a well-established metal-nanoparticle catalyst preparative protocol by simultaneous in situ metal NP and nanospace organization (PSSO) with 1,4-bis(trimethylsilyl)-1,4-dihydropyrazine (Si-DHP) as a strong reducing agent. SAFe(0) was easy to handle in air and could be recycled with a low iron-leaching rate in reaction cycles.

We have developed cycloisomerization between an aryl vinyl ether and a functionalized alkyne, such as silylalkyne, to give 2,3-disubstituted benzofuran derivatives using [IrCl(cod)]2, PCy3, and NaBArF4. This catalyst system not only catalyzes the above cycloisomerization but also isomerize a terminal olefin to give an aryl vinyl ether.

Liquid biopsy is a non-invasive tool to examine the genetic profile of tumors by identification of mutated circulating tumor DNA (ctDNA), which is often analyzed by next generation sequencing (NGS) or droplet digital PCR (ddPCR) assay. We first examined the ctDNA mutation in pre-operative plasma samples obtained from 154 colorectal cancer (CRC) and 46 gastric cancer (GC) patients, using the NGS-based panel assay. The overall detection rate of mutated ctDNA was 72.0% (144 of 200 patients), and the panel-based screening identified 207 and 47 mutations from CRC and GC patients, respectively. The ddPCR analysis was then performed on post-operative samples of 77 patients, and detection of mutated ctDNA was earlier than imaging-based diagnosis in all of 6 patients who showed the tumor recurrences after surgery. Our data also revealed that patients with positive post-operation ctDNA level showed significant shorter recurrence-free survival compared to the patients with negative ctDNA level (HR 14.9; 95% CI, 0.7-313.5; p < 0.0001). These findings suggested that screening of mutated ctDNA by liquid biopsy aids in identifying the patients at high risk of post-operative recurrence, and serial screening of ctDNA would allow to monitor the response after treatment and/or early detection of tumor recurrence.

Pyrolyzed iron-containing polyaniline (C-Fe-PANI) is one of the most promising candidates as a non-precious metal based electrocatalyst for oxygen reduction reaction (ORR). Although the ORR activity depends on the surface area arisen from pyrolysis-generated micropores on C-Fe-PANI particles, the micropore generation is hindered by pyrolysis-formed iron nanoparticles (Fe NPs) embedded inside C-Fe-PANI particles. Here, we demonstrate the pyrolysis of iron-containing PANIs under suppression of micropore-generation hindrance by blocking the Fe NPs formation. The higher-molecular-weight (MW: 100,000) PANI was dispersed in an FeCl3 solution before pyrolysis for preventing FeCl3 penetration inside PANI particles. As a result, as compared to the case of lower-MW (5,000) PANI, the Fe NPs formation was more suppressed inside catalyst particles to give 1.9 (1.8) times micropore volume (specific surface area), leading to a 11 % higher current density in ORR electrocatalytic performance test in acidic media.

[Image: see text] We designed and synthesized a novel 1,2-deoxy-pyranose and terminal epoxide methyl substituted derivatives of spliceostatin A using Julia–Kocienski olefination as a key step. With respect to the biological activity, the 1,2-deoxy-pyranose analogue of spliceostatin A suppressed AR-V7 expression at the nano level (IC(50) = 3.3 nM). In addition, the in vivo toxicity test showed that the 1,2-deoxy-pyranose analogue was able to avoid severe toxicity compared to spliceostatin A.

To achieve a complete closed-shell quinoidal state, bis(dicyanomethylene)-substituted quinoidal terthiophenes bearing benzene annelation at all thiophene rings were synthesized using a retro-Diels–Alder reaction as the key step. The unique structures and properties originating from the full benzene annelation were revealed by X-ray analysis as well as property measurements. Organic solar cells based on the combination of a donor polymer with a quinoidal terthiophene as an acceptor showed a power conversion efficiency of 1.39%.

We report on the absorption, fluorescence, and two-photon excitation spectra of a series of 5-phenylisoindolo[2,1-a]quinoline dyes. Depending on the substituents, we observed increasing two-photon absorption cross sections, with values up to 56 GM@973 nm, which are similar to those of the enhanced green fluorescent protein and fluorescein, common fluorescent chromophores.

The synthesis of helically chiral [6]helicene-based sulfonic acid and sulfonamide from enantiomerically pure 1-acetylthio-5,6,9,10-tetrahydro[6]helicene is reported. The first helically chiral disulfonimides were developed as a synthetic application of [6]helicene-based sulfonamide. This new class of organocatalysts was tested in an asymmetric Mukaiyama aldol reaction to obtain up to quantitative yields and enantioselectivities up to 24%.

We show that N,N-dimethylformamide-stabilized Pd nanoclusters (NCs) have high catalytic activity in the reaction of substituted 2-iodoanilines with alkynes to give 2,3-disubstituted indoles. This indole synthesis does not require phosphine ligands and proceeds with low Pd catalyst loadings. The Pd NCs were separated from the mixture after the reaction, and recycled at least three times. Transmission electron microscopy images showed that the Pd particle size before the reaction was 1.5–2.5 nm. The particle size after the reaction was 2–3 nm. X-ray photoelectron spectroscopy showed that the binding energy of the Pd NCs before the reaction was 335.0 eV.

Sucrose is well known as naturally occurring sweeteners. Photoreactive sucrose derivative containing 3-(trifluoromethyl) diazirinyl moiety is designed for photoaffinity labeling. As 1'-hydroxyl group of sucrose is well known to be less reactive than other primary alcohols, the optimization of reaction conditions for diazirinyl benzyl bromide derivative at sucrose 1'-postion was examined to elucidate the functional analysis of sweet receptors.

The desymmetrization of meso compounds is one of the most effective strategies for asymmetric synthesis. This digest focuses on recent progress in the desymmetrization of meso-diols and their derivatives. The topics discussed here include methods for the enzymatic acylation of meso-diols and the hydrolysis of meso-diesters, acylation, related reactions of meso-diols with organocatalysts and metal catalysts, the oxidation of meso-diols by enzymes, organocatalysts, and metal catalysts, and the desymmetrization of meso-dicarbamates with metal catalysts. The desymmetrization of meso-diols using tandem reactions is also discussed.

A new tridentate N3 ligand (TMG3tach) consisting of cis,cis-1,3,5-triaminocyclohexane (tach) and three N,N,N′,N′-tetramethylguanidino (TMG) groups has been developed to prepare copper complexes with a tetrahedral geometry and a labile coordination site. Treatment of the ligand with CuIIX2 (X = Cl and Br) gave copper(II)-halide complexes, [CuII(TMG3tach)Cl]+ (2Cl) and [CuII(TMG3tach)Br]+ (2Br), the structures of which have been determined by X-ray crystallographic analysis. The complexes exhibit a four-coordinate structure with C3v symmetry, where the labile halide ligand (X) occupies a position on the trigonal axis. 2Br was converted to a methoxido-copper(II) complex [CuII(TMG3tach)(OMe)](OTf) (2OMe), also having a similar four-coordinate geometry, by treating it with an equimolar amount of tetrabutylammonium hydroxide in methanol. The methoxido-complex 2OMe was further converted to the corresponding phenolato-copper(II) (2OAr) and thiophenolato-copper(II) (2SAr) complexes by ligand exchange reactions wit...

The synthesis and optical resolution of helically chiral 5,6,9,10-tetrahydro-1-[6]helicenethiol and its subsequent transformations to enantiopure 1-sulfur-functionalized [6]helicenes are reported. A novel enantiopure [7]thiahelicene having a thiophene ring at the terminal position of the [6]helicene skeleton was synthesized.

N-propylsulfanyl and isopropylsulfanyl substituted 2,5-di(1,3-dithiol-2-ylidene)-1,3-dithiolane-4-thione derivatives with methoxycarbonyl groups were synthesized, and their redox and electronic properties and crystal structures were investigated. Solid-state absorption spectra showed that both derivatives absorb almost all visible light. Furthermore isopropylsulfanyl-substituted derivatives absorb near-infrared light and the absorption edge reaches around 1320 nm. The crystal structures show that both derivatives are stacked in one dimension to form a columnar structure, but the molecular arrangements of their columns were quite different from each other. The stacked n-propylsulfanyl derivatives kept their orientation of thiocarbonyl groups in the same direction and the one molecule of the isopropylsulfanyl derivatives were rotated in relation to each other by an angle of 56° about their longer molecular axis. The TD-DFT calculation of stacked molecules suggests that the molecular arrangement among the st...

We have developed two novel, isomeric compounds of phenyl-substituted dinaphtho[2,3-b:2′,3′-d]furan (Ph-DNF-VW and Ph-DNF-VV) using a facile synthetic protocol. Notably, Ph-DNF-VW has been shown to...

Phenylthiourea (PTU) is well known as bioactive compound and one of the reversible inhibitors for tyrosinase. Tyrosinase plays very important roles for tyrosine metabolisms to maintain the skin homeostasis from sunlight with forming melanin. Synthesis of photoaffinity label reagents of PTU will be attractive thesis to elucidate functional analysis for tyrosinase.

A new class of solution-processable thieno[3,2-f:4,5-f′]bis[1]benzothiophene (TBBT-V) semiconductors are investigated. Semiconductors with decyl substituents and two kinds of π-extended decylthienyl substituents are facially derivatized from functionalized dibromo-substituted TBBT-Vvia either a Negishi or a Stille cross coupling procedure. The solubilities of TBBT-V semiconductors are somewhat higher than those of their previously developed dinaphtho[2,3-b:2′,3′-d]thiophene (DNT-V) counterparts. Single crystal analysis together with a calculation study on the transfer integral and the band structure in decyl-substituted TBBT-V (C10-TBBT-V) clarifies that these semiconductors form two-dimensionally ordered herringbone packing structures and the effective mass in the columnar direction rivals that of the previously developed decyl-substituted DNT-V. The carrier mobilities of TBBT-V derivatives in solution grown into single-crystalline films are remarkable (up to 6.2 cm2 V−1 s−1). Furthermore, their operation voltages are apparently lower than those of previously developed DNT-V derivatives due to the optimized ionization potential of the TBBT-V core and further π-extension by substitution of the thienyl groups.

We execute electron density analysis of SrTiO3 at low temperatures up 80 K and high pressures up to 11.88 GPa using X-ray single-crystal diffraction and ab initio quantum chemical molecular orbital (MO) calculation. By changing pressures, the cubic SrTiO3 with perovskite structure goes through a antiferroelastic distortion to tetragonal symmetry above the critical pressure Pc=7 GPa with c/a 1 and increasing with lowering temperature. Difference Fourier (D-F) synthesis experimentally proves the residual electron densities Δρ(xyz) are associated with two different effects: electron hybridization bonding electron and anharmonic thermal vibration atoms. The d–p–π hybridization between Ti(3d) and O(2p) orbitals is confirmed in the residual electron density, which is deformed from the ideal spherical density conducted by the atomic scattering factor fi using Hartree–Fock (HF) approximation. MO calculation also reveals the electron hybridization. Anharmonic thermal vibration of atoms yields a large effect to the structure transition. Mulliken charges analysis of MO calculation indicates much smaller charges than their formal ionic charges. Their ionicity increases from cubic to tetragonal above Pc and below Tc.

We report the catalysis of a Sonogashira–Hagihara cross-coupling reaction using a DMF-stabilized copper nanoparticle catalyst. The reaction proceeded with low catalyst loadings, and a turnover number of 4.0 × 103 was recorded for 0.01 mol% catalyst loading. DMF-stabilized copper nanoparticles thus showed high catalytic activity.

Laparoscopic percutaneous extraperitoneal closure (LPEC) in boys is more complex than in girls, because the vas deferens and testicular vessels must be separated from the peritoneum. We therefore developed a needle-shaped surgical instrument that enables blunt separation. Here, we report the effectiveness of this new device.The new device is a ligature carrier consisting of (1) an inner tube (19-G blunt needle) through which slides a rod with a loop wire at its tip that can catch and release suture materials and (2) an outer tube (17-G needle) with a cutting edge. The blunt-structured inner tube enables blunt separation. All actions (stabbing, separation, and catching) in the LPEC procedure that are required to close the hernia orifice using a thread are facilitated through a simple small incision by switching between the inner and outer tubes.From January 2013 to September 2015, 73 boys with inguinal hernia or hydrocele underwent LPEC, and the new device was used in 45 of these cases. We compared surgical results between cases wherein the new (group A) and conventional devices (LPEC needle; group B) were used.The mean surgery duration was 33.4 and 34.8 min for groups A and B, respectively. Neither group experienced complications during or after surgery.Our findings suggest that the newly developed needle device may improve the safety of the LPEC procedure for boys, although further investigation involving more cases and long-term follow-up is needed in the future.

We have synthesized and theoretically calculated 5-methylisoindolo[2,1-a]quinoline derivatives as novel near-infrared absorption dyes via a ruthenium-catalyzed one-pot metathesis/oxidation/1,3-dipolar cycloaddition protocol. The reactivity in 1,3-dipolar cycloaddition was governed by the electronic effect of aromatic ring substituents. Substrates with an electron-withdrawing group on the aromatic ring afforded higher yields. The maximal absorption wavelength of 3,5-dimethyl-11-phenylisoindolo[2,1-a]quinoline-7,10-dione and 11-(4-methoxyphenyl)-5-methylisoindolo[2,1-a]quinoline-7,10-dione in MeOH increased to 736 and 737 nm, although that of 3a was 727 nm.

We have investigated the intrinsic thermoelectric properties of epitaxial β-FeSi2 thin films and the impact of phosphorus (P) doping. Epitaxial β-FeSi2 thin films with single phase were grown on Si(111) substrates by two different techniques in an ultrahigh-vacuum molecular beam epitaxy (MBE) system: solid-phase epitaxy (SPE), where iron silicide films formed by codeposition of Fe and Si at room temperature were recrystallized by annealing at 530°C to form epitaxial β-FeSi2 thin films on Si(111) substrates, and MBE of β-FeSi2 thin films on epitaxial β-FeSi2 templates formed on Si(111) by reactive deposition epitaxy (RDE) at 530°C (RDE + MBE). Epitaxial SPE thin films based on codeposition had a flatter surface and more abrupt β-FeSi2/Si(111) interface than epitaxial RDE + MBE thin films. We investigated the intrinsic thermoelectric properties of the epitaxial β-FeSi2 thin films on Si(111), revealing lower thermal conductivity and higher electrical conductivity compared with bulk β-FeSi2. We also investigated the impact of doping on the Seebeck coefficient of bulk and thin-film β-FeSi2. A route to enhance the thermoelectric performance of β-FeSi2 is proposed, based on (1) fabrication of thin-film structures for high electrical conductivity and low thermal conductivity, and (2) proper choice of doping for high Seebeck coefficient.

Two 1-[6]helicenol derivatives were synthesized by Ni-catalyzed [2+2+2] cycloaddition on a multigram scale. Both enantiomers of the 1-[6]helicenols could be efficiently prepared by simple optical resolution. As a synthetic application of helically chiral 1-[6]helicenols, a novel class of [6]helicene-based phosphinites was developed; these compounds represent the first examples of helically chiral phosphinite ligands. Up to 90 % ee was obtained for the Pd-catalyzed asymmetric allylic alkylation reaction.

Background Accurate and prompt diagnosis is required for the primary evaluation of pediatric appendicitis. Among pediatricians and surgeons working in Yamanashi Prefecture, the pediatric appendicitis medical information (PAMI) sheet was edited in April 2011 to reflect the diagnostic results of the pediatric primary and emergency medical service and used as a referral document for surgical consultation to secondary hospitals. Methods The PAMI sheet consisted of sections for history taking, symptoms, physical signs and laboratory findings without a scoring system. For 32 consecutive months starting in April 2011, 59 patients hospitalized for suspected appendicitis were retrospectively reviewed. In particular, a total of 17 referral patients evaluated with the PAMI sheet were assessed in order to evaluate the utility of the form. Results The pediatric surgeons were able to easily determine patient condition from the PAMI sheet. In total, 13 of 17 patients had appendicitis. According to the physical findings of the 17 studied patients, the judgment of right lower quadrant tenderness (κ = 0.63) and guarding (κ = 1.00) was consistent between the pediatric surgeons and primary attending pediatricians. Conclusions The PAMI sheet aids in the collection of detailed history and objective data with a high level of accuracy, and provides useful referral diagnostic information to the secondary-level hospitals.

New bis(ene-1,2-dithiolato)-oxido-alcoholato molybdenum(VI) and -oxido-thiolato molybdenum(VI) anionic complexes, denoted as [Mo(VI)O(ER)L2](-) (E = O, S; L = dimethoxycarboxylate-1,2-ethylenedithiolate), were obtained from the reaction of the corresponding dioxido-molybdenum(VI) precursor complex with either an alcohol or a thiol in the presence of an organic acid (e.g., 10-camphorsulfonic acid) at low temperature. The [Mo(VI)O(ER)L2](-) complexes were isolated and characterized, and the structure of [Mo(VI)O(OEt)L2](-) was determined by X-ray crystallography. The Mo(VI) center in [Mo(VI)O(OEt)L2](-) exhibits a distorted octahedral geometry with the two ene-1,2-dithiolate ligands being symmetry inequivalent. The computed structure of [Mo(VI)O(SR)L2](-) is essentially identical to that of [Mo(VI)O(OR)L2](-). The electronic structures of the resulting molybdenum(VI) complexes were evaluated using electronic absorption spectroscopy and bonding calculations. The nature of the distorted O(h) geometry in these [Mo(VI)O(EEt)L2](-) complexes results in a lowest unoccupied molecular orbital wave function that possesses strong π* interactions between the Mo(d(xy)) orbital and the cis S(p(z)) orbital localized on one sulfur donor from a single ene-1,2-dithiolate ligand. The presence of a covalent Mo-S(dithiolene) bonding interaction in these monooxido Mo(VI) compounds contributes to their low-energy ligand-to-metal charge transfer transitions. A second important d-p π bonding interaction derives from the ∼180° O(oxo)-Mo-E-C dihedral angle involving the alcoholate and thiolate donors, and this contributes to ancillary ligand contributions to the electronic structure of these species. The formation of [Mo(VI)O(OEt)L2](-) and [Mo(VI)O(SEt)L2](-) from the dioxidomolybdenum(VI) precursor may be regarded as a model for the active-site formation process that occurs in the dimethyl sulfoxide reductase family of pyranopterin molybdenum enzymes.

N-Alkyl-N-(2-vinylbenzyl)prop-2-en-1-amine derivatives undergo a one-pot olefin isomerization/aliphatic enamine ring-closing metathesis (RCM)/oxidation/1,3-dipolar cycloaddition sequence with the ruthenium complex, Ru(CO)HCl(PPh3)3, a second generation Hoveyda–Grubbs catalyst, and a 1,3-dipolarophile. Overall, in a single operation the reaction sequence converts simple benzylamine derivatives into isoindolo[1,2-a]isoquinolines with a π-conjugated four-ring system, through three unique ruthenium-catalyzed transformations.

Catalytic activity of [Os(III)(OH)(H2O)(L-N4Me2)](PF6)2 (1: L-N4Me2 = N,N'-dimethyl-2,11-diaza-[3,3](2,6)pyridinophane) in 1,2-cis-aminohydroxylation of alkenes with sodium N-chloro-4-methylbenzenesulfonamide (chloramine-T) is explored. Simple alkenes as well as those containing several types of substituents are converted to the corresponding 1,2-aminoalcohols in modest to high yields. The aminoalcohol products have exclusively cis conformation with respect to the introduced -OH and -NHTs groups. The spectroscopic measurements including cold mass spectroscopic study of the reaction product of complex 1 and chloromine-T as well as density functional theory (DFT) calculations indicate that an oxido-aminato-osmium(V) species [Os(V)(O)(NHTs)(L-N4Me2)](PF6)2 (2) is an active oxidant for the aminohydroxylation. The DFT calculations further indicate that the reaction involves a [3 + 2] cycloaddition between 2 and alkene, and the regioselectivity in the aminohydroxylation of unsymmetrical alkenes is determined by the orientation that bears less steric hindrance from the tosylamino group, which leads to the energetically more preferred product isomer.

We discuss the synthesis of cuboid-monoclinic tungsten oxide (C-m-WO3) particles and hexagonal-plate-like-hexagonal tungsten oxide (H-h-WO3) particles by acidification and hydrothermal treatment with (NH4)10W12O41·5H2O as a starting material. From the WO3 particles, thin- and thick-film gas sensors were fabricated for NO2 sensing applications and the effect of the morphology and crystal structure of the WO3 particles on the NO2 sensing properties was investigated. The extremely high sensor responses of 160 to 20 ppb NO2 and 10 120 to 500 ppb NO2 were obtained for a C-m-WO3 thin-film sensor at an operating temperature of 200 °C. The crystal structure features of as-prepared particles were studied by XRD, XPS, SEM, TEM, and solid state 1H and 13C NMR measurements. The presence of residual impurities, cations, and high density of surface OH− in the H-h-WO3 particles was demonstrated, which could be one of the key reasons for the crystal structure dependence of the sensing properties in C-m-WO3 and H-h-WO3 gas sensors.

A 2-month-old full-term female infant developed nasal stridor, which progressed to respiratory distress and poor sucking ability. Direct pharyngoscopy showed laryngomalacia and a midline cystic mass in the lingual region. The mass pressed on the epiglottis, causing dyspnea. Computed tomography incidentally revealed extralobar pulmonary sequestration. Direct deroofing of the lingual cyst and plication of the epiglottis were performed at 3 months of age, and the patient recovered from the respiratory distress. Histopathology of the cystic mass showed a thyroglossal duct cyst. Thoracoscopic resection of the pulmonary sequestration was then done at 17 months of age. Thyroglossal duct cysts in the lingual region may cause destabilization of the epiglottis and laryngomalacia, resulting in acquired respiratory obstruction. The combination of thyroglossal duct cyst, laryngomalacia, and pulmonary sequestration is rare; therefore, reports must be accumulated in order to explore the embryological origins of such cases.

The one-pot reactions of catalytically generated bicyclic zinc enolate with various electrophiles are reported. The zinc enolate as a key intermediate is efficiently delivered from Ni-catalyzed reductive cyclization of alkynyl cyclohexadienone. Employing aldehydes, imine, nitroalkene, and α,β-unsaturated carbonyl compounds as electrophiles, this new class of one-pot reactions gave multi-functionalized cis-hydrobenzofurans and octahydro-4,7-ethanobenzofuran-9-one derivatives in moderate to good yields.