Search

Nishimura K., Xu S., Nishii Y., et al. One-Step Synthesis of Benzophosphole Derivatives from Arylalkynes by Phosphenium-Dication-Mediated Sequential C-P/C-C Bond Forming Reaction. Organic Letters. 25(9), 1503-1508, 10 March 2023; © 2023 American Chemical Society. https://doi.org/10.1021/acs.orglett.3c00263., A metal-free, phosphenium-dication-mediated sequential C-P and C-C bond forming reaction has been developed. This protocol can provide concise access to the (di)benzophosphole derivatives in one synthetic operation from the readily available and simple arylalkynes and phosphinic acids. Application to the multiple cyclization reaction and the fully intermolecular three-component-coupling-type reaction are also described.

This is the accepted version of the following article: Nakamura Shotaro, Okubo Kohei, Nishii Yuji, et al. Stimuli‐Responsive Properties on a Bisbenzofuropyrazine Core: Mechanochromism and Concentration‐Controlled Vapochromism. Chemistry – A European Journal, e202302605 (2023), which has been published in final form at https://doi.org/10.1002/chem.202302605. This article may be used for non-commercialpurposes in accordance with the Wiley Self-ArchivingPolicy [https://authorservices.wiley.com/author-resources/Journal-Authors/licensing/self-archiving.html], Stimulus-responsive organic materials with luminescence switching properties have attracted considerable attention for their practical applications in sensing, security, and display devices. In this paper, bent-type bisbenzofuropyrazine derivatives, Bent-H and Bent-sBu, with good solubilities were synthesized, and their physical and optical properties were investigated in detail. Bent-H gave three crystalline polymorphs, and they showed different luminescence properties depending on their crystal packing structures. In addition, Bent-H exhibited mechanochromic luminescence in spite of its rigid skeleton. Bent-sBu exhibited unique concentration-dependent vapochromic luminescence. Ground Bent-sBu was converted to blue-emissive, green-emissive, and green-emissive high-viscosity solution states at low, moderate, and high concentrations of CHCl3 vapor, respectively. This finding represents a concentration-dependent multi-phase transition with an organic solvent, which is of potent interest for application in sensing systems.

The nitrogen atom is ubiquitous in bioactive molecules and functional materials, and the development of new CN bond forming strategies is thus one of the long-standing research subjects in the synthetic community. This account describes the nitrogen-umpolung-enabled copper-catalyzed highly chemo- and stereoselective amination protocols developed by the author’s research group. Starting from the CH amination, electrophilic amination of stable organoboron and organosilicon compounds, aminoboration/hydroamination of alkenes, and their applications to the synthesis of functionality-rich alkylamines are shown. The reaction design, concept, and substrate scope are briefly summarized.

A copper-mediated trifluoromethylthiolation of alkenyl iodides with AgSCF₃ has been developed. CuSCF₃ species generated in-situ from a copper salt and AgSCF₃ can be coupled with alkenyl iodides to produce the corresponding trifluoromethylthioalkenes efficiently. The reaction conditions are compatible with various functional groups. Moreover, its scale-up synthesis is also possible to provide the desired trifluoromethylthiolated product even on a gram-scale.

Kojima Y., Nishii Y., Hirano K.. Ligand-Enabled Copper-Catalyzed Regio- and Stereoselective Allylboration of 1-Trifluoromethylalkenes. Organic Letters. 24(40), 7450-7454, 14 October 2022; https://doi.org/10.1021/acs.orglett.2c03024., A copper-catalyzed regio- and stereoselective allylboration of 1-trifluoromethylalkenes with bis(pinacolato)diboron (pinB-Bpin) and allylic chlorides has been developed to form functionalized trifluoromethylated products with high diastereoselectivity. The key to success is the judicious choice of Cs2CO3 base and t-Bu-modified dppe-type ligand, which enables the otherwise challenging high catalyst turnover and suppression of the competing defluorination side reaction from an alkylcopper intermediate. The product derivatization of the resulting Bpin moiety can deliver diverse CF3-containing molecules with high stereochemical fidelity.

Tokura Y., Xu S., Kojima Y., et al. Pd-catalysed, Ag-assisted C2-H alkenylation of benzophospholes. Chemical Communications 58, 12208 (2022); https://doi.org/10.1039/D2CC04942B ., A palladium-catalysed, silver-assisted regioselective C2-H alkenylation of benzophospholes with terminal alkenes has been developed. The palladium catalysis accommodates styrenes and electron-deficient alkenes including ester, ketone, nitrile, and phosphonate. Thus, this protocol enables the rapid construction of various benzophosphole-vinylene conjugations from the two simple C-H starting substrates. Optical properties of newly synthesized C2-alkenylated benzophospholes are also investigated.

Asai K., Hirano K., Miura M.. Palladium-Catalyzed Benzylic Silylation of Diarylmethyl Carbonates with Silylboranes under Base-Free Conditions. European Journal of Organic Chemistry 2022, e202101535 (2022); https://doi.org/10.1002/ejoc.202101535., A palladium-catalyzed benzylic silylation of diarylmethyl carbonates with silylboranes has been developed. The reaction proceeds smoothly even under external base-free conditions, and the corresponding benzylic silanes are formed in good to high yields. The obtained benzyl silane derivatives can work as the benzylic nucleophiles by the action of a suitable fluoride source and react with some carbon electrophiles to deliver the corresponding benzylic C−C cross-coupled products. Additionally, while still preliminary, the allylic silylation of the isoelectronic allylic carbonates is also achieved.

Xu S., Nishimura K., Saito K., et al. Palladium-catalysed C-H arylation of benzophospholes with aryl halides. Chemical Science 13, 10950 (2022); https://doi.org/10.1039/d2sc04311d., A palladium-catalysed C-H arylation of benzophospholes with aryl halides has been developed. The reaction with aryl iodides and bromides proceeds well even under phosphine ligand-free Pd(OAc)2 catalysis whereas the Pd(PCy3)2 is effective for the coupling with less reactive aryl chlorides. The optimal conditions are also applicable to the double arylations with organic dihalides and annulation reaction with ortho-dihalogenated benzenes, making the corresponding benzophosphole-based acceptor-donor-acceptor-type molecules and highly condensed heteroacene-type molecules of potent interest in materials chemistry. Although there are many reports of catalytic C-H functionalisations of related benzoheteroles such as indoles, benzothiophenes, and benzofurans, this is the first successful example of the catalytic direct C-H transformation of benzophospholes, to the best of our knowledge. The preliminary optoelectronic properties of some newly synthesized benzophosphole derivatives are also investigated.

Asai K., Miura M., Hirano K.. Palladium-Catalyzed Cross-Coupling Reaction of Diarylmethanol Derivatives with Diborylmethane. Journal of Organic Chemistry. 87(11), 7436-7445, (2022), 3 June 2022; © 2022 American Chemical Society. https://doi.org/10.1021/acs.joc.2c00715., A palladium-catalyzed cross-coupling reaction of diarylmethanol derivatives with diborylmethane has been developed. The reaction proceeds chemoselectively to deliver the corresponding homobenzylic boronates in good yields.

Hirano K., Miura M.. Hydroamination, Aminoboration, and Carboamination with Electrophilic Amination Reagents: Umpolung-Enabled Regio- and Stereoselective Synthesis of N-Containing Molecules from Alkenes and Alkynes. Journal of the American Chemical Society. 144(2), 648-661, (2022), 19 January 2022; © 2022 American Chemical Society. https://doi.org/10.1021/jacs.1c12663., Nitrogen (N) is ubiquitously found in bioactive molecules, pharmaceutical agents, and organic functional materials. Accordingly, development of new C–N bond-forming catalysis has been one of the long-standing research subjects in synthetic organic chemistry. In this Perspective, recent advances in highly selective amination reactions with electrophilic amination reagents are described: by taking advantage of the concept of nitrogen umpolung, otherwise challenging aminofunctionalizations, such as hydroamination, aminoboration, and carboamination, of readily available feedstock-like alkenes and alkynes are possible, giving densely functionalized complex and often chiral alkylamines with high selectivity. The scope, limitations, and reaction mechanism are briefly summarized.

The authors have developed a large capacity rotary compressor with compact size and low vibration. Recently, we have strong requirements for larger capacity without changing the compressor shell diameter. Considering for larger capacity in conventional 2-cylinder rotary compressor inverter type, there are issues such as high vibration, big sound. As the solution for these problems, we have developed 3-cylinder rotary compressor inverter type which have different compression process of 120 ° phase per revolution for each cylinder. The developed compressor achieves a capacity target, proves one-quarter vibration level comparing with 2-cylinder rotary compressor and ensure the improvement of reliability result. We have been manufacturing the world largest capacity of new rotary compressor and have been launching into the market since September 2020. This new model has successfully attained more large capacity with same shell diameter as our previous large capacity of 2-cylinder rotary compressor inverter type. This new model adopt some new technologies such as the 3-cylinder design for balancing rotation torque, the multi discharge valve structure, the integrated bearing with partition plate and the new wide-range motor. By these technologies, the outdoor units of multiple air conditioner for buildings (Variable Refrigerant Flow-VRF) can achieve a large capacity 20 HP (56kW) with applying one compressor unit only.

Kajiwara R., Xu S., Hirano K., et al. Bipyridine-Type Bidentate Auxiliary-Enabled Copper-Mediated »C-H/C-H Biaryl Coupling of Phenols and 1,3-Azoles. Organic Letters. 23(14), 5405-5409, (2021), 16 July 2021; © 2021 American Chemical Society. https://doi.org/10.1021/acs.orglett.1c01735., A copper-mediated dehydrogenative C-H/C-H biaryl coupling of phenols and 1,3-azoles has been developed. The key to its success is the introduction of a bipyridine-type bidentate auxiliary, 4,4′-di(tert-butyl)-2,2′-bipyridine, on the phenol oxygen, which is readily prepared and easily attachable, detachable, and recyclable. The reaction proceeds smoothly in the presence of copper salt alone to form the corresponding phenol-azole heterobiaryls, which are prevalent motifs in functional molecules such as excited-state intramolecular proton transfer materials.

Hazra S., Hirano K., Miura M.. Rhodium-Catalyzed C4-Selective C-H Alkenylation of 2-Pyridones by Traceless Directing Group Strategy. Organic Letters. 23(4), 1388-1393, (2021), 19 February 2021; © 2021 American Chemical Society. https://doi.org/10.1021/acs.orglett.1c00050., A rhodium-catalyzed C4-selective C-H alkenylation of 3-carboxy-2-pyridones with styrenes has been developed. The carboxylic group at the C3 position works as the traceless directing group, and the corresponding C4-alkenylated 2-pyridones are obtained exclusively with concomitant decarboxylation. Unlike the reported procedures, the exclusive C4 selectivity is uniformly observed even in the presence of potentially more reactive C-H bonds at the C5 and C6 positions. By using this strategy, the multiply substituted 2-pyridone can be prepared via sequential C-H functionalization reactions.

A Cu-mediated ortho-selective CH cyanation of phenols with ethyl cyanoformate as the cyano source has been developed. The key to success is the introduction of 4,4¤-di-tert-butyl-2,2¤-bipyridine (dtbpy) bidentate auxiliary on the phenol oxygen, which is easily attachable, detachable, and recyclable. The newly developed protocol is tolerant of several carbonyl functional groups, which are incompatible with previous Lewis-acid-promoted cyanation of phenols.

The authors have developed a large capacity rotary compressor with compact size and low vibration. Recently, we have strong requirements for larger capacity without changing the compressor shell diameter. Considering for larger capacity in conventional 2-cylinder rotary compressor inverter type, there are issues such as high vibration, big sound. As the solution for these problems, we have developed 3-cylinder rotary compressor inverter type which have different compression process of 120 ° phase per revolution for each cylinder. The developed compressor achieves a capacity target, proves one-quarter vibration level comparing with 2-cylinder rotary compressor and ensure the improvement of reliability result. We have been manufacturing the world largest capacity of new rotary compressor and have been launching into the market since September 2020. This new model has successfully attained more large capacity with same shell diameter as our previous large capacity of 2-cylinder rotary compressor inverter type. This new model adopt some new technologies such as the 3-cylinder design for balancing rotation torque, the multi discharge valve structure, the integrated bearing with partition plate and the new wide-range motor. By these technologies, the outdoor units of multiple air conditioner for buildings (Variable Refrigerant Flow-VRF) can achieve a large capacity 20 HP (56kW) with applying one compressor unit only.

Kumiko Kato,1 Maki Takeuchi,1 Yuka Yonekawa,1 Yuzen Kashima,1 Koji Hirano,2 Mineo Kondo1 1Department of Ophthalmology, Mie University Graduate School of Medicine, Tsu, Japan; 2Department of Ophthalmology, Fujita Health University Bantane Hospital, Nagoya, JapanCorrespondence: Kumiko KatoDepartment of Ophthalmology, Mie University Graduate School of Medicine, 2-174 Edobashi, Tsu, Mie, 514-8507, JapanTel +81-59-231-5027Fax +81-59-231-3036Email k-kato@clin.medic.mie-u.ac.jpPurpose: To report our findings in three cases of an inflamed conjunctival nevus whose size and degree of pigmentation were reduced by topical antiallergic and immunosuppressive ophthalmic solutions.Methods: Observational case series. Three patients with inflamed conjunctival nevus were examined by slit-lamp biomicroscopy, and the findings before and after the treatments were compared.Results: All three patients had a slightly pigmented and edematous conjunctival tumor at the corneal limbal area. The tumors were hyperemic, and papillae and follicles were present on the superior conjunctiva in all patients. All of the patients had an allergic predisposition. The antiallergic treatment not only resolved the hyperemia and edema of the palpebral conjunctiva, but also reduced the tumor size. In one case, the topical antiallergic agent alone led to a reduction of the tumor size. A combination of topical antiallergic agent and topical immunosuppressant was effective in reducing the tumor size and degree of pigmentation in the other two patients.Conclusion: The hyperemia and pigmentation in eyes with inflamed conjunctival nevus can be resolved by topical antiallergic agent and topical immunosuppressant without resection of the tumor.Keywords: inflamed juvenile conjunctival nevus, epinastine, tacrolimus

Koji Hirano,1 Hidenori Tanaka,2 Kumiko Kato,3 Kaoru Araki-Sasaki4 1Department of Ophthalmology, Fujita Health University Bantane Hospital, Nagoya, Aichi, 454-8509, Japan; 2Department of Ophthalmology, Fujita Health University School of Medicine, Toyoake, Aichi, 470-1192, Japan; 3Department of Ophthalmology, Mie University Graduate School of Medicine, Tsu, Mie, 514-8507, Japan; 4Department of Ophthalmology, Kansai Medical University, Hirakata, Osaka, 573-1010, JapanCorrespondence: Koji HiranoDepartment of Ophthalmology, Fujita Health University Bantane Hospital, 6-10, Otoubashi 3-cho-me, Nakagawa-ku, Nagoya, Aichi, 454-8509, JapanTel +81-52-321-8171Fax +81-52-322-4734Email kojihira@fujita-hu.ac.jpPurpose: In clinical practice we sometimes encounter patients with severe corneal ulcers who have been treated with topical corticosteroids. This study reviewed the clinical features and visual outcomes of these patients and investigated the background of the prescription of topical corticosteroids.Patients and Methods: The medical records of patients who visited the Cornea Service at Fujita Health University Bantane Hospital and were treated for infectious keratitis from April 2016 to March 2020 were retrospectively reviewed. Patients treated with topical corticosteroids before a culture-proven diagnosis were studied in terms of demographics, best-corrected visual acuity at arrival and at last visit, the clinical course after visit, ocular history, and combination therapy by the previous ophthalmologist.Results: Out of the 200 eyes of 197 patients with infectious keratitis, 14 eyes of 14 patients were treated with topical corticosteroids before a culture-proven diagnosis. All 14 patients were referred, as they had severe keratitis that could not be cured with topical antibiotics and corticosteroids. Based on the culture results, we diagnosed Acanthamoeba keratitis (AK) in six patients, fungal keratitis (FK) in two patients, bacterial keratitis (including a suspected case) i

Nishimura K., Hirano K., Miura M.. Direct Synthesis of Dibenzophospholes from Biaryls by Double C-P Bond Formation via Phosphenium Dication Equivalents. Organic Letters. 22(8), 3185-3189, (2020), 17 April 2020; © 2020 American Chemical Society. https://doi.org/10.1021/acs.orglett.0c00944., We have developed a new strategy for the generation of phosphenium dication equivalents from readily available phosphinic acids and Tf2O. The in situ-generated dication equivalents can be readily coupled with simple (hetero)biaryls to form the corresponding dibenzophospholes directly. This protocol can also be applied to the concise synthesis of six- A nd seven-membered phosphacycles as well as the largely Ï-extended heteroacene derivatives, which are of great interest in the field of organic functional materials.

Matsude A., Hirano K., Miura M.. Highly Stereoselective Synthesis of 1,2-Disubstituted Indanes by Pd-Catalyzed Heck/Suzuki Sequence of Diarylmethyl Carbonates. Organic Letters. 22(8), 3190-3194, (2020), 17 April 2020; © 2020 American Chemical Society. https://doi.org/10.1021/acs.orglett.0c00945., A palladium-catalyzed Mizoroki-Heck-type cyclization/Suzuki-Miyaura cross-coupling cascade of diarylmethyl carbonates with arylboronic acid derivatives has been developed to deliver the corresponding 1,2-disubstituted indanes in good yields with high diastereoselectivity (trans/cis > 20:1). The key to achieve the high chemoselectivity and stereoselectivity is the use of the tris[3,5-di(tert-butyl)-4-methoxyphenyl]phosphine (DTBMP) ligand of remote steric hindrance. Moreover, the asymmetric synthesis is possible by the enantiospecific, stereoinvertive reaction of the optically active starting substrates to form the chiral indanes with high stereochemical fidelity (>98% es).

Kajiwara R., Takamatsu K., Hirano K., et al. Copper-Mediated Regioselective C-H Sulfenylation and Selenation of Phenols with Phenanthroline Bidentate Auxiliary. Organic Letters. 22(15), 5915-5919, (2020), 7 August 2020; © 2020 American Chemical Society. https://doi.org/10.1021/acs.orglett.0c02012., A copper-mediated, phenanthroline-directed highly ortho-selective C-H sulfenylation of phenols with diaryl disulfides proceeds to form the corresponding unsymmetrical diaryl sulfides in good yield. The key to success is the introduction of a phenanthroline directing group of the bidentate-chelating nature, which is easily attachable, detachable, and even recyclable. Moreover, the same strategy is applicable to the C-H selenation, giving the diaryl selenides with high efficiency and regioselectivity.

Kato Y., Otomura N., Hirano K., et al. Synthesis of DPPP- And DPPPEN-Type Bidentate Ligands by Ring-Opening Diphosphination of Methylene- And Vinylcyclopropanes under Visible-Light-Promoted Photoredox Catalysis. Journal of Organic Chemistry. 85(9), 5981-5994, (2020), 1 May 2020; © 2020 American Chemical Society. https://doi.org/10.1021/acs.joc.0c00417., A ring-opening diphosphination of methylene- and vinylcyclopropanes with tetraaryldiphosphines (Ar2P-PAr2) has been developed to afford the corresponding 1,3-diphenylphosphinopropane- and 1,3-diphenylphosphinopentane-type bidentate ligands, respectively. The reaction proceeds under bromine cation-initiated, visible-light-promoted photoredox catalysis at ambient temperature. Owing to the ready availability of functionalized diphosphines, the electronically diverse MeO- and CF3-substituted bidentate ligands are also easily prepared.

This is the accepted version of the following article: Matsude A., Hirano K., Miura M.. Palladium-Catalyzed Intramolecular Mizoroki-Heck-Type Reaction of Diarylmethyl Carbonates. Advanced Synthesis and Catalysis 362, 518 (2020), which has been published in final form at https://doi.org/10.1002/adsc.201901398. This article may be used for non-commercialpurposes in accordance with the Wiley Self-ArchivingPolicy [https://authorservices.wiley.com/author-resources/Journal-Authors/licensing/self-archiving.html], A palladium-catalyzed intramolecular Mizoroki-Heck-type reaction of diarylmethyl tert-butyl carbonates has been developed. The reaction proceeds under external base-free, neutral conditions to form the corresponding methyleneindanes in good yields only with liberation of CO2 and tBuOH. The resulting exo-methylene moiety is reactive and thus a good synthetic handle for further manipulations. Additionally, the asymmetric synthesis is also possible through a Pd/chiral Mandyphos ligand-mediated kinetic resolution. To the best of our knowledge, this is the first successful example of catalytic enantioselective Mizoroki-Heck-type reaction of secondary benzyl electrophiles. (Figure presented.).

A copper-catalyzed regioselective hydrodefluorination of 1-trifluoromethylalkenes with hydrosilanes has been developed. The copper catalysis is compatible with several functional groups, including alkyl chloride, ether, ester, nitrile, and imide moieties, to form the corresponding gem-difluoroalkenes in good yields. Additionally, asymmetric induction is also possible by using the chiral DTBM-SEGPHOS ligand, and gem-difluoroalkene with point chirality at the allylic position is obtained with high enantioselectivity.

Hirano K., Miura M., Xu S.. Pd-catalyzed regioselective C−H alkenylation and alkynylation of allylic alcohols with the assistance of a bidentate phenanthroline auxiliary. Organic Letters. 22(22), 9059-9064, (2020), 20 November 2020; © 2020 American Chemical Society. https://doi.org/10.1021/acs.orglett.0c03444., A Pd-catalyzed regioselective C−H alkenylation of allylic alcohols with electron-deficient alkenes has been developed. The key to success is the introduction of bidentately coordinating phenanthroline directing group, which enables the otherwise challenging and regioselective C−H activation at the proximal alkenyl C−H bonds over the conceivably competitive allylic C−O bond activation. The same Pd/phenanthroline system is efficient for the C−H alkynylation of allylic alcohols with alkynyl bromides.

Hirano K., Miura M., Asai K.. Divergent synthesis of isonitriles and nitriles by palladium- catalyzed benzylic substitution with TMSCN. Journal of Organic Chemistry. 85(19), 12703-12714, (2020), 2 October 2020; © 2020 American Chemical Society. https://doi.org/10.1021/acs.joc.0c01861., Ligand-controlled palladium-catalyzed divergent synthesis of isonitriles and nitriles from benzylic carbonates and TMSCN has been developed. The BINAP- or DPEphos-ligated palladium catalyst selectively provides the corresponding benzylic isonitriles, whereas their regioisomers, benzylic nitriles, are formed exclusively under phosphine ligand-free conditions. Mechanistic studies reveal that isonitrile is the primary product under both conditions, but it is isomerized into nitrile in the absence of ancillary phosphine ligands.

Takamatsu K., Hayashi Y., Kawauchi S., et al. Copper-Catalyzed Regioselective C-H Amination of Phenol Derivatives with Assistance of Phenanthroline-Based Bidentate Auxiliary. ACS Catalysis. 9(6), 5336-5344 (2019), 7 June 2019; © 2019 American Chemical Society. https://doi.org/10.1021/acscatal.9b01145., A copper-catalyzed regioselective direct amination of phenol derivatives with diarylamines via phenanthroline-based bidentate auxiliary-directed C-H cleavage has been developed. This reaction proceeds smoothly with only a copper salt and air as a terminal oxidant to produce the corresponding o-aminophenols in good yields. Moreover, the directing group can be easily attached, detached, and recycled. Additionally, preliminary computational studies of the reaction with DFT have also been performed.

This is the accepted version of the following article: Xu S., Takamatsu K., Hirano K., et al. Synthesis of Seven-Membered Benzolactones by Nickel-Catalyzed C−H Coupling of Benzamides with Oxetanes. Chemistry - A European Journal 25, 9400 (2019), which has been published in final form at https://doi.org/10.1002/chem.201900543. This article may be used for non-commercialpurposes in accordance with the Wiley Self-ArchivingPolicy [https://authorservices.wiley.com/author-resources/Journal-Authors/licensing/self-archiving.html], A NiCl2(PEt3)2-catalyzed regioselective C−H coupling of 8-aminoquinoline-derived benzamides with oxetanes has been developed. The reaction proceeds with concomitant removal of the 8-aminoquinoline auxiliary to directly form the corresponding seven-membered benzolactones, which frequently occur in natural products and bioactive molecules. Additionally, no stereochemical erosion is observed during the course of the reaction, and the use of enantioenriched and substituted oxetane thus provides a new avenue to the optically active benzolactone.

Takamatsu K., Hayashi Y., Kawauchi S., et al. Copper-Mediated Decarboxylative C–H Arylation of Phenol Derivatives with ortho-Nitrobenzoic Acids Using Phenanthroline-Based Bidentate Auxiliary. ChemistrySelect 4, 11833 (2019); https://doi.org/10.1002/slct.201902860., A copper-mediated decarboxylative C–H arylation of phenol derivatives with ortho-nitrobenzoic acid salts via phenanthroline-directed C–H cleavage has been developed. The N,N-bidentate phenanthroline auxiliary uniquely promotes the reaction only in the presence of a copper salt to produce the corresponding biaryls in acceptable yields. Moreover, the directing group can be easily introduced and removed. Additionally, preliminary computational mechanistic studies with DFT have also been performed.

This is the accepted version of the following article:Hazra S., Hirano K., Miura M.. Solvent-Controlled Rhodium-Catalyzed C6-Selective C−H Alkenylation and Alkylation of 2-Pyridones with Acrylates. Asian Journal of Organic Chemistry 8, 1097 (2019), which has been published in final form at https://doi.org/10.1002/ajoc.201900190. This article may be used for non-commercialpurposes in accordance with the Wiley Self-ArchivingPolicy [https://authorservices.wiley.com/author-resources/Journal-Authors/licensing/self-archiving.html], A solvent-controlled rhodium-catalyzed C6-selective alkenylation and alkylation of 2-pyridones with acrylates via a pyridine-directed C−H cleavage was developed. Using DMF as solvent, the C−H alkenylation with acrylates selectively occurs to deliver the corresponding C6-alkenylated 2-pyridones in good yields. On the other hand, the C6-alkylated products are predominantly formed in a more polar and protic solvent, HFIP. Thus, a single set of starting substrates can be divergently transformed to C6-functionalized 2-pyridones, which are of potent interest in medicinal and pharmaceutical chemistry.

Hazra S., Hirano K., Miura M.. Pyridine-directed Rh-catalyzed C6-selective C–H acetoxylation of 2-pyridones. Heterocycles 101, 223 (2020); https://doi.org/10.3987/com-19-s(f)16., A Rh(III)-catalyzed C-H acetoxylation of 2-pyridones with phenyliodine(III) diacetate (PIDA) in a DCE/AcOH mixed solvent system has been developed using N-2-pyridyl function as directing group. The reaction occurs under mild conditions, typically in air at 40 oC, to selectively produce the corresponding C6-acetoxylated 2-pyridones in moderate to good yields.

Kato Y., Otomura N., Hirano K., et al. Diphosphination of ortho-quinone methide precursors with diphosphines. Tetrahedron Letters 60, 2014 (2019); https://doi.org/10.1016/j.tetlet.2019.06.055., A fluorine anion-mediated diphosphination of ortho-quinone methide precursors (2-(chloromethyl)silyloxybenzenes) with diphosphines has been developed. The reaction proceeds smoothly under mild conditions (CH2Cl2 solvent, 0 °C) to form the corresponding 2-(phosphinomethyl)oxyphosphinobenzenes, which are potential bidentate ligands in metal catalysis. Additionally, some mechanistic investigations are also performed.

Koji Hirano,1 Hidenori Tanaka,1,2 Kumiko Kato,3 Kaoru Araki-Sasaki4 1Department of Ophthalmology, Ban Buntane Hotokukai Hospital, School of Medicine, Fujita Health University, Nagoya, Aichi 454-8509, Japan; 2Department of Ophthalmology, School of Medicine, Fujita Health University, Toyoake, Aichi 470-1192, Japan; 3Department of Ophthalmology, Mie University School of Medicine, Tsu, Mie 514-8507, Japan; 4Department of Ophthalmology, Japan Community Health Care Organization Hoshigaoka Medical Center, Hirakata, Osaka 573-8511, Japan Background: Deep anterior lamellar keratoplasty (DALK) is indicated to correct high astigmatism in patients with keratoconus (KC) and no evidence of Descemet’s membrane rupture. However, some patients with KC experience graft rejection-like inflammatory reactions within 2 months (usually in the first week) after DALK. The aim of this study was to identify the characteristics and influencing factors of these reactions by reviewing the records of patients who underwent DALK or penetrating keratoplasty (PKP) for KC or other corneal problems.Methods: We retrospectively reviewed the medical records of patients who underwent DALK for KC (DALK/KC), PKP for KC (PKP/KC), or DALK for other corneal problems (DALK/non-KC) at Ban Buntane Hotokukai Hospital between January 2006 and December 2015 and who were followed for more than 1 year. We collected data on the characteristics and incidence of severe inflammatory graft reactions in the early postoperative phase (ie, within 2 months after keratoplasty) and visual outcomes after these inflammatory reactions.Results: Postoperative inflammatory reactions characterized by persistent epithelial defects, loose suture with infiltration, and vessel invasion occurred in seven of eleven DALK/KC patients, three of 50 DALK/non-KC patients, and none of five PKP/KC patients. These reactions were nonresponsive to topical steroids, and suture removal was required. Although a clear corneal graft in the pupilla

Kaoru Araki-Sasaki,1 Yasuhiro Osakabe,2 Koji Fujita,2 Kazunori Miyata,3 Koji Hirano4 1Department of Ophthalmology, Japan Community Health Care Organization, Hoshigaoka Medical Center, Hirakata, Japan; 2Department of Molecular Pathology, Tokyo Medical University, Tokyo, Japan; 3Department of Ophthalmology, Miyata Eye Hospital, Miyakonojo, Japan; 4Department of Ophthalmology, Ban Buntane Hotokukai Hospital, Fujita Health University, Nagoya, Japan Abstract: We describe the histological changes in the collagen fibers of a 50-year-old male who presented keratoconus with secondary corneal amyloidosis. Corneal tissue from the patient was obtained following a penetrating keratoplasty and was subjected to histochemical analysis using Masson’s trichrome staining, Congo red staining, anti-lactoferrin antibody, and anti-transforming growth factor-beta-induced protein (TGFBIp) antibody. A Congo red-positive region was detected in the anterior half of the stroma in the center and inferior cornea. Although hemotoxylin and eosin staining revealed irregularity in the Congo red-positive region, other parts of the stroma did not show any abnormalities. Positive staining both by anti-TGFBIp and anti-lactoferrin antibodies was observed in the Congo red-positive region. Interestingly, all the layers of the corneal stroma, including the peripheral region, were positively stained by anti-TFGBIp antibody, even in the Congo red-negative area. Masson’s trichrome staining also showed irregular staining throughout the corneal stroma, even outside of the Congo red-positive region. Additionally, Bowman’s layer, which consists of collagen type IV, was damaged. TGFBIp was strongly expressed and Masson’s trichrome staining was reduced throughout the entire keratoconic stroma. The constant qualitative changes in keratoconic collagen fibers, along with the observed abnormality in the Bowman’s membrane, might point to the pathogenesis of secondary corne

identifier:http://igakkai.kms-igakkai.com/wp/wp-content/uploads/1997en/23(2)49-54.1997.pdf

Koji Hirano,1 Mihoko Koide,2 Yoshikazu Mizoguchi,3 Yasuhiro Osakabe,4 Kaoru-Araki Sasaki5 1Department of Ophthalmology, Ban Buntane Hotokukai Hospital, School of Medicine, Fujita Health University, Nagoya, Japan; 2Koide Internal Medicine and Eye Clinic, Nagoya, Japan; 3Department of Pathology, Ban Buntane Hotokukai Hospital, School of Medicine, Fujita Health University, Nagoya, Japan; 4Department of Molecular Pathology, Tokyo Medical University, Tokyo, Japan; 5Department of Ophthalmology, Japan Health Care Organization, Hoshigaoka Medical Center, Hirakata, Japan Purpose: Leukoplakia is the term given to a white patch or plaque that is found mainly on the oral mucus membrane. It can occasionally be seen on the corneal surface. We report our clinical and histopathological findings in a case of unilateral corneal leukoplakia. Methods: A 26-year-old woman was referred to our hospital because of a white patch on her right cornea that continued to expand. She first noticed the white patch when she was 20 years old, and the white patch had expanded to cover the pupillary area affecting her vision. After plastic surgery on both eyelids for bilateral entropion to alleviate the pain caused by the eyelashes rubbing the cornea, the white corneal patch decreased in size. Because of this reduction, we performed surgery to remove the patch with microforceps under topical anesthesia. The plaque was removed easily and completely, and submitted for histopathological examination. Results: Histopathological examination showed that the specimen had characteristics of epidermis with a basal cell layer, spinous cell layer, granular cell layer, and horny layer with hyperkeratosis. She was diagnosed with leukoplakia of the corneal surface. The basic structure of the squamous cell layer was preserved, and there were no signs of metaplasia. Six months after the removal of the leukoplakia, no recurrence was seen and her corrected decimal visual acuity recovered to 1.0. Conclusion: Our case of

Kaoru Araki-Sasaki,1 Yasuhiro Osakabe,2 Hideki Fukuoka,3 Ryuichi Ideta,4 Koji Hirano5 1Department of Ophthalmology, Japan Community Health Care Organization, Hoshigaoka Medical Center, Hirakata, 2Department of Molecular Pathology, Tokyo Medical University, Tokyo, 3Department of Ophthalmology, Kyoto Prefectural University of Medicine, Kyoto, 4Ideta Eye Hospital, Kumamoto, 5Department of Ophthalmology, Ban Buntane Hotokukai Hospital, School of Medicine, Fujita Health University, Nagoya, Japan Purpose: To describe observations by ultrahigh-resolution optical coherence tomography (OCT) in a secondary corneal amyloidosis (SCA) patient with histological analysis of excised tissue. A unique finding under OCT of her fellow eye is also described.Case: A 39-year-old female had suffered from trichiasis in both of her eyes for more than 30 years. Slit-lamp examination showed a milky-white soft mass on her left cornea and a linear opacity on the fellow cornea at the cilia-attached region. OCT demonstrated the presence of a mass region within a thin epithelial layer and no destruction of Bowman’s layer in her left cornea. In the fellow cornea, which exhibited a linear opacity, a high-density spot in Bowman’s layer was observed at the cilia-attached region covered by the epithelial layer, with normal thickness. Histological examination of the excised cornea showed that the mass was positive with both Congo red and antilactoferrin antibody.Conclusion: SCA, amyloid gradually accumulates above Bowman’s layer, occupying the epithelial layer, with no destruction of Bowman’s layer until the advanced stage. A high-density spot in Bowman’s layer might be the first stage of SCA. Keywords: OCT, secondary corneal amyloidosis, lactoferrin, cornea

Kumiko Kato,1 Koji Hirano,2 Tetsuro Nagasaka,3 Koichi Matsunaga,1 Yuko Takashima,1 Mineo Kondo1 1Department of Ophthalmology, Mie University School of Medicine, Tsu, Japan; 2Department of Ophthalmology, Fujita Health University, Nagoya, Japan; 3Department of Medical Laboratory Science, Nagoya University Graduate School of Medicine, Nagoya, Japan Purpose: To report the histopathological findings in a case of severe Acanthamoeba sclerokeratitis (ASK). Patient and methods: A 46-year-old patient was referred to the Department of Ophthalmology of Mie University Hospital because of a severe corneal ulcer of the right eye of 6 months' duration. Our initial examination showed a ring-shaped corneal opacity with extensive epithelial defects and nodular scleritis. Cysts of Acanthamoeba were identified in cultures from corneal scrapings, and he was diagnosed with ASK. He was started on antiamoebic treatment, including topical micafungin and chlorhexidine. The corneal ulcer was debrided several times. One month later, he developed necrotizing scleritis, and the cornea suddenly perforated. The eye was enucleated because of severe pain and prepared for histopathological examination. Results: The histopathological examination showed an infiltration of polymorphonuclear leukocytes throughout the corneal stroma and also in the limbal area of the sclera, forming an abscess. Granulation tissue was observed in the anterior sclera close to the ciliary body, but the posterior regions of the eye were not affected by inflammation or tissue destruction. The cysts of Acanthamoeba were observed only in the cornea. Conclusion: Histopathological examination of an eye with severe ASK showed that the inflammation and tissue granulation were present only in the anterior part of eye, and the posterior segment was not affected. Because the inflammation and tissue destruction were confined to the anterior segment, enucleation might not have been necessary if the severe pain was able to be cont

After the Great East Japan Earthquake, it is an urgent necessity for us to cut down the vain use of the power. Beforehand we have proposed the reduction of the power consumption used in “actual” air-conditioner operating load is low, and we have produced Dual rotary compressor can make only one of two compression units run (in the following, refer as “Dual system”) and provide high efficiency since 2004 and have made still better of it1). This time we developed another Dual rotary compressor with a new mechanism. To put Dual system in practice, the compression units have one of two vanes pushed into and pulled apart its roller depending on conditions. As compared with the conventional dual compressor has the way of controlling pressure in the cylinder in order to balance pressure of the compression unit inside with that of the case inside and rear of the vane, the new one has the different method of doing so. Being still applied the idea of balance of pressure, a new mechanism controls pressure at the rear of the vane. We expanded it into 1-suction piping twin rotary compressor is our unique production and developed the new dual compressor. This new compressor bettered by 3% of Annual Performance Factor (APF) efficiency in Japan than that of our conventional model and the air-conditioner with it can cool and heat operation by minimum 45W, and it has been produced since Oct. 2011. And it will be expected to load except air-conditioners with itself because it can run until high compression ratio under low capacity operation in comparison to the same size compressor.

After the Great East Japan Earthquake, it is an urgent necessity for us to cut down the vain use of the power. Beforehand we have proposed the reduction of the power consumption used in “actual” air-conditioner operating load is low, and we have produced Dual rotary compressor can make only one of two compression units run (in the following, refer as “Dual system”) and provide high efficiency since 2004 and have made still better of it1). This time we developed another Dual rotary compressor with a new mechanism. To put Dual system in practice, the compression units have one of two vanes pushed into and pulled apart its roller depending on conditions. As compared with the conventional dual compressor has the way of controlling pressure in the cylinder in order to balance pressure of the compression unit inside with that of the case inside and rear of the vane, the new one has the different method of doing so. Being still applied the idea of balance of pressure, a new mechanism controls pressure at the rear of the vane. We expanded it into 1-suction piping twin rotary compressor is our unique production and developed the new dual compressor. This new compressor bettered by 3% of Annual Performance Factor (APF) efficiency in Japan than that of our conventional model and the air-conditioner with it can cool and heat operation by minimum 45W, and it has been produced since Oct. 2011. And it will be expected to load except air-conditioners with itself because it can run until high compression ratio under low capacity operation in comparison to the same size compressor.

Nickel catalysis enables us to develop new reactions with trialkylboranes and silacyclobutanes of modest reactivity. A combination of Ni(cod)2 and tri-tert-butylphosphine catalyses alkylation reactions of aldehydes and a, b-unsaturated esters with various trialkylboranes of modest reactivity, suppressing conceivable b-hydride elimination from alkylnickel intermediates. A nickel catalyst is also useful for 1, 4-addition of bis(pinacolato)diboron to a, b-unsaturated esters and amides. Nickel-catalysed reaction of silacyclobutanes with aldehydes results in ring opening to afford the corresponding alkoxyallylsilanes. In contrast, the ring expansion reaction of benzosilacyclobutene with aldehydes yields benzoxasilacyclohexenes. A nickel catalyst prepared from Ni(cod)2 and tricyclohexylphosphine realises direct silylation of terminal alkenes with silacyclobutane furnishing vinylsilanes.