Viewed: 18:02:24 in March 30, 2020

Keywords: Ni; Mn; cod; dtbpy; NMP; EPR; 読みたい論文シリーズ; 有機化学; ブログ

Nickel-Catalyzed Intermolecular Carbobromination of Alkynes (Takahashi, Toshifumi; Kurahashi, Takuya; Matsubara, Seijiro)
ACS Catal. 2020, 10 (6), 3773−3777.

ニッケル触媒下での内部アルキンと臭化アリールの反応に関する論文のようです。β-ブロモスチレン化合物が生成します。

内部アルキンと臭化アリールの反応といえば、アリール基がアルキンに付加してβ–水素脱離とかで、「臭化」の方はどこかに行ってしまう(大体は塩になる)のが常。ところがこの論文の反応では臭素原子もアルキンのsp炭素と結合しており、その炭素–臭素結合がマンガン還元剤やニッケル触媒にも耐えている。この現象がなんとも不思議で、反応系中で何が起きているのか知りたく、読みたい論文に追加しました。

この個人的に謎な反応、要旨テキスト中では系中で発生した高原子価のニッケル種[Ni(III)]の寄与によるものと説明されており、Supporting Information中にもNi(III)前駆体であるNi(I)の存在を確認するためのEPR測定のデータがあるなど、色々考察されており、推定される触媒サイクルが本文中に記されていると期待されますので、反応機構を中心に、本文を読んで色々確認したいところです。Z体が優先して生成する理由も。

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☆s軌道

原子を構成している電子の軌道の1つ。雑に言えば球のような形。
「(いろんな意味での)大きさ」にあわせて、1s軌道, 2s軌道, 3s軌道, …と呼ばれる。
水素原子は1s軌道に電子を1つ、ヘリウム原子は1s軌道に電子を2つ持つ。リチウム原子は1s軌道に2つ、2s軌道に1つ。

 

Just finished the calculations: 2-hydroxy-5-(trifluoromethyl)pyridine https://t.co/tqy3mRNH3m pic.twitter.com/SFyHfYKKdA

— nanoniele (@nanoniele) March 23, 2020

 

　

 

新型コロナ／原油・非鉄、下値に警戒　現金化・ドル高で下押し圧力
(日刊工業新聞)
https://www.nikkan.co.jp/artic...

米アバンティＲ＆Ｄと電通大、車の大気影響“見える化”　デンマークで来月実証
(日刊工業新聞)
https://www.nikkan.co.jp/artic...

ＮＩＣＴ先端研究／情通機構（127）量子ドット高品質化、高温下で光通信可能に
(日刊工業新聞)
https://www.nikkan.co.jp/artic...

3月11日までは通常だった
(村井君のブログ)
http://murai-kun.cocolog-nifty...

次元を切り替える―フォスフォレン内のエキサイティングな励起子
(沖縄科学技術大学院大学)
https://www.oist.jp/ja/news-ce...

異常な翻訳停滞の強制終了を試験管内で再現　〜リボソームのユビキチン化による新生ペプチド鎖の運命決定機構〜
(東北大学)
https://www.tohoku.ac.jp/japan...

自動運転の経路計画プログラムから危険動作を自動検出する手法を開発 ～細かい指定をせずに、現実的かつ危険な動作を発見する～
(国立情報学研究所)
https://www.nii.ac.jp/news/rel...

【研究発表】もと湿地の水田が洪水の発生を抑制する 〜生態系を利用した防災・減災を考慮した土地利用の実現に貢献〜
(首都大学東京)
https://www.tmu.ac.jp/news/top...

ＡＩ画像認識アルゴリズムを搭載した光学顕微鏡を開発 ～ 原子層を積み重ねた新規材料開発を大幅加速 ～
(東京大学)
https://www.iis.u-tokyo.ac.jp/...

小惑星探査機「はやぶさ2」観測成果論文の Science 誌掲載について
(名古屋大学)
http://www.nagoya-u.ac.jp/abou...

日本全国440火山の情報がひとめでわかるウェブ総合システムを開発 －世界的にも高精度な「20万分の1日本火山図」データベースを公開－
(産業技術総合研究所)
https://www.aist.go.jp/aist_j/...

アルコール綿　購入
(ある女性研究者の日記)
https://sunnily.exblog.jp/3111...

イロイロ不足しています
(研究室日記　Heaven helps those who help themselves.　天は自ら助くる者を助く)
https://polyphenol.exblog.jp/2...

70万人のゲノムによるリスク予測で、高血圧・肥満が現代人の寿命を最も縮めていることを特定 －生まれつきの遺伝情報を使って、誰でも治療可能な健康要因を解明する－
(理化学研究所)
https://www.riken.jp/press/202...

[ChemBioChem 2020, 21, 623−627]
Unveiling Two Consecutive Hydroxylations: Mechanisms of Aromatic Hydroxylations Catalyzed by Flavin‐Dependent Monooxygenases for the Biosynthesis of Actinorhodin and Related Antibiotics
(Hashimoto, Makoto; Taguchi, Takaaki; Ishikawa, Kazuki; Mori, Ryuichiro; Hotta, Akari; Watari, Susumu; Katakawa, Kazuaki; Kumamoto, Takuya; Okamoto, Susumu; Ichinose, Koji)

[ChemBioChem 2020, 21, 656−662]
Development of Fluorogenic Probes for Rapid High‐Contrast Imaging of Transient Nuclear Localization of Sirtuin 3
(Gao, Jingchi; Hori, Yuichiro; Shimomura, Takashi; Bordy, Mathieu; Hasserodt, Jens; Kikuchi, Kazuya)

[ChemElectroChem 2020, 7, 1261−1276]
Electrocatalytic Oxidation of Hydroxide Ions by Co₃O₄ and Co₃O₄@SiO₂ Nanoparticles Both at Particle Ensembles and at the Single Particle Level
(Xie, Ruo‐Chen; Volokhova, Maria; Boldin, Aleksei; Seinberg, Liis; Tsujimoto, Masahiko; Yang, Minjun; Rasche, Bertold; Compton, Richard G.)

[ChemSusChem 2020, 13, 929−937]
Optimizing Electron Densities of Ni‐N‐C Complexes by Hybrid Coordination for Efficient Electrocatalytic CO₂ Reduction
(Wang, Zhong‐Li; Choi, Jaecheol; Xu, Mingquan; Hao, Xianfeng; Zhang, Hao; Jiang, Zheng; Zuo, Ming; Kim, Jeonghun; Zhou, Wu; Meng, Xianguang; Yu, Qing; Sun, Zhihu; Wei, Shiqiang; Ye, Jinhua; Wallace, Gordon G.; Officer, David L.; Yamauchi, Yusuke)

[Chem. Asian. J. 2020, 15, 573−576]
Iron‐Catalyzed Radical Cleavage/C−C Bond Formation of Acetal‐Derived Alkylsilyl Peroxides
(Shiozaki, Yoko; Sakurai, Shunya; Sakamoto, Ryu; Matsumoto, Akira; Maruoka, Keiji)

[Chem. Asian. J. 2020, 15, 581−584]
Solid‐State [2+2] Photodimerization of 1‐Aryl‐4‐pyridylbutadienes in Cation‐π‐Controlled Crystals
(Yamada, Shinji; Aya, Kanae)

[Chem. Asian. J. 2020, 15, 590−593]
Ionic Dopant‐Encapsulating Single‐Walled Carbon Nanotube Films with Metal‐Like Electrical Conductivity
(Iihara, Yu; Kawai, Tsuyoshi; Nonoguchi, Yoshiyuki)

[Chem. Asian. J. 2020, 15, 594−600]
Inhibition of Ligand Binding Ability of Three Porphyrins by an Organic Effector
(Nishimura, Tomoaki; Sasaki, Yoshito; Tachi, Yoshimitsu; Suzuki, Shuichi; Okada, Keiji; Kozaki, Masatoshi)

[Chem. Asian. J. 2020, 15, 601−605]
Luminescent Coordination Polymers Constructed from a Flexible, Tetradentate Diisopyrazole Ligand and Copper(I) Halides
(Yoneda, Tomoki; Kasai, Chika; Manabe, Yumehiro; Tsurui, Makoto; Kitagawa, Yuichi; Hasegawa, Yasuchika; Sarkar, Parantap; Inokuma, Yasuhide)

[Chem. Sci. 2020, 11, 2934−2942]
Electron spin polarization generated by transport of singlet and quintet multiexcitons to spin-correlated triplet pairs during singlet fissions
(Matsuda, Saki; Oyama, Shinya; Kobori, Yasuhiro)
Tag: SF, OSC, OFC

[Chem. Sci. 2020, 11, 3028−3035]
Site-selective [2 + 2 + n] cycloadditions for rapid, scalable access to alkynylated polycyclic aromatic hydrocarbons
(Kiel, Gavin R.; Bergman, Harrison M.; Tilley, T. Don)
Tag: AM, C, CA

[Org. Biomol. Chem. 2020, 18, 2129−2138]
In situ air oxidation and photophysical studies of isoquinoline-fused N-heteroacenes
(Sonawane, Amol D.; Sonawane, Rohini A.; Win, Khin Myat Noe; Ninomiya, Masayuki; Koketsu, Mamoru)
Tag: Fe, IMD, imH, Him, imid, oxidn., bim, 91-22-5

[Lab Chip 2020, 20, 1083−1091]
Highly sensitive mutation quantification by high-dynamic-range capillary-array electrophoresis (HiDy CE)
(Anazawa, Takashi; Matsunaga, Hiroko; Yamamoto, Shuhei; Inaba, Ryoji)
Tag: CAE, WT, Sn

[J. Mater. Chem. B 2020, 8, 2233−2237]
Surfaces immobilized with oligo-prolines prevent protein adsorption and cell adhesion
(Noguchi, Yuri; Iwasaki, Yasuhiko; Ueda, Masato; Kakinoki, Sachiro)
Tag: P, Pro, COL

[ACS Sens. 2020, 5, 338−345]
Transcutaneous Blood VOC Imaging System (Skin-Gas Cam) with Real-Time Bio-Fluorometric Device on Rounded Skin Surface
(Iitani, Kenta; Toma, Koji; Arakawa, Takahiro; Mitsubayashi, Kohji)
Tag: NAD, lb, SC, ADH, FL, H, Sn, UV, CH3CH2OH, NA, nic, A, VOC, LE, LED, EtOH

[ACS Sens. 2020, 5, 431−439]
Avian Influenza Virus Detection by Optimized Peptide Termination on a Boron-Doped Diamond Electrode
(Matsubara, Teruhiko; Ujie, Michiko; Yamamoto, Takashi; Einaga, Yasuaki; Daidoji, Tomo; Nakaya, Takaaki; Sato, Toshinori)
Tag: HA, EIS, BDD, IS, PFU, B, EC, CT, Sn, DL, IAV, BDDE, IV, EIS

[J. Phys. Chem. C 2020, 124, 5978−5986]
Effect of Help-Guest Size and Hydrogen Bonding on the Stability of N-Methylpiperidine Structure H Clathrate Hydrate
(Kondo, Yuri; Alavi, Saman; Murayama, Kotaro; Ruiz, Ahmad; Takeya, Satoshi; Ohmura, Ryo)
Tag: PXRD, lb, Fe, Et, H, GM, Sn, XR, NMP, 626-67-5, MDS, Nme, MD, C2H6, pip, PIPD, Me, XRD, CH4, HB, HB

[J. Phys. Chem. C 2020, 124, 6054−6062]
What Is the Active Site for the Oxidative Coupling of Methane Catalyzed by MgO? A Metadynamics-Biased Ab Initio Molecular Dynamics Study
(Ishikawa, Atsushi; Tateyama, Yoshitaka)
Tag: R, Sn, O, AIMD, OCM, MD, C2H6, FES, ABMD, C, CH4, GS

[J. Phys. Chem. C 2020, 124, 6103−6109]
Electrocatalytic Effect on the Photon-to-Current Conversion Efficiency of Gold-Nanoparticle-Loaded Titanium(IV) Oxide Plasmonic Electrodes for Water Oxidation
(Onishi, Tatsuhiro; Teranishi, Miwako; Naya, Shin-ichi; Fujishima, Musashi; Tada, Hiroaki)
Tag: EM, GNP, pptn., AuNP, NWA, Au, EC, Sn, WO, ECA, oxidn., WOR, NP, NC, NW, curr., Cat

[J. Phys. Chem. C 2020, 124, 6110−6120]
Probing Functionalities and Acidity of Calcined Phenylene-Bridged Periodic Mesoporous Organosilicates Using Dynamic Nuclear Polarization NMR, Diffuse Reflectance Infrared Fourier Transform Spectroscopy, and X-ray Photoelectron Spectroscopy
(Pirez, Cyril; Nagashima, Hiroki; Dumeignil, Franck; Lafon, Olivier)
Tag: PXRD, DNP, PE, DRIFTS, ES, Fe, PMO, Pr, Al, XPS, IMD, imH, Him, imid, XR, EM, FT, PhH, BZ, oxidn., COOH, DRIFT, PS, PhOH, Ph, XRD, TEM, e-, IR, Cat

[J. Phys. Chem. C 2020, 124, 6121−6129]
Catalytic Properties of Chemically Modified Graphene Sheets to Enhance Etching of Ge Surface in Water
(Mikurino, Ryo; Ogasawara, Ayumi; Hirano, Tomoki; Nakata, Yuki; Yamashita, Hiroto; Li, Shaoxian; Kawai, Kentaro; Yamamura, Kazuya; Arima, Kenta)
Tag: PR, CE, C, O, oxidn., NH2, 302-01-2, CMG, NH3, GO, ORR

[J. Phys. Chem. C 2020, 124, 6304−6310]
Molecular Weight Induced Conformational Change and Its Impact on β-Phase Formation of Polydiarylfluorene in Dilute Solution
(Nagai, Masaru; Liu, Jie; Huang, Wei; Kikuchi, Moriya; Kawaguchi, Seigou; Xie, Linghai)
Tag: PF, IC, SLS, LS, PFN, dil., HMW, FL, Sn, GPC, Ar

[J. Phys. Chem. C 2020, 124, 6364−6370]
Selenium Substitution Enhances Reverse Intersystem Crossing in a Delayed Fluorescence Emitter
(Drummond, Bluebell H.; Hoover, Gabrielle C.; Gillett, Alexander J.; Aizawa, Naoya; Myers, William K.; McAllister, Bryony T.; Pu, Yong-Jin; Credgington, Dan; Seferos, Dwight S.)
Tag: ISC, RISC, おーれっど, FL, ES, ESR, em, Sn, Se, S, TPA, DF, NH2, OLED, LE, Ph, e-, LED

[J. Phys. Chem. B 2020, 124, 2116−2123]
Enhancement of Oxidative Reaction by the Intramolecular Electron Transfer between the Coordinated Redox-Active Metal Ions in SOD1
(Ohyama, Takumi; Kuroi, Kunisato; Wakabayashi, Taiyu; Fujimaki, Nobuhiro; Nakabayashi, Takakazu)
Tag: ALS, IET, ET, SOD, SOD, oxidn., ORC, e-, Cat

[J. Phys. Chem. B 2020, 124, 2209−2217]
Space Size-Dependent Transformation of Tetraphenylethylene Carboxylate Aggregates by Ice Confinement
(Miyagawa, Akihisa; Harada, Makoto; Fukuhara, Gaku; Okada, Tetsuo)
Tag: aq., det., TPE, FLT, Et, FL, em, Sn, 57-13-6, 57-50-1, Ph, C2H4, AIE

[J. Phys. Chem. A 2020, 124, 2253−2263]
Infrared Spectra of Isomers of Protonated Aniline in Solid para-Hydrogen
(Tsuge, Masashi; Chen, Yu-Hsuan; Lee, Yuan-Pern)
Tag: det., ANI, Sn, QC, Mat, ABS, expt., e-, IR

[J. Phys. Chem. A 2020, 124, 2328−2334]
Microcanonical Nucleation Theory for Anisotropic Materials Validated on Alumina Clusters
(Chemin, Arsène; Miyajima, Ken; Melinon, Patrice; Mafuné, Fumitaka; Amans, David)
Tag: thermodn., expt., GS

[ACS Photonics 2020, 7, 554−561]
AlGaN Deep-Ultraviolet Light-Emitting Diodes Grown on SiC Substrates
(SaifAddin, Burhan K.; Almogbel, Abdullah S.; Zollner, Christian J.; Wu, Feng; Bonef, Bastien; Iza, Michael; Nakamura, Shuji; DenBaars, Steven P.; Speck, James S.)
Tag: EQE, QE, est., N, Sn, UV, DUV, LE, LEE, TF, LED, TDD

[ACS Photonics 2020, 7, 673−679]
Reconfigurable Surface Plasmon Resonance Photodetector with a MEMS Deformable Cantilever
(Oshita, Masaaki; Takahashi, Hidetoshi; Ajiki, Yoshiharu; Kan, Tetsuo)
Tag: PD, Au, Sn, expt., curr.

[ACS Photonics 2020, 7, 845−852]
Excitation Dynamics in Layered Lead Halide Perovskite Crystal Slabs and Microcavities
(Fujiwara, Kentaro; Zhang, Shuai; Takahashi, Shun; Ni, Limeng; Rao, Akshay; Yamashita, Kenichi)
Tag: esp., TRPL, Fe, TR, PL, Sn, TA, ET, ABS, expt., LE, LHP, e-, LED, P

[Bioconjugate Chem. 2020, 31, 547−553]
Stimulating Macropinocytosis for Intracellular Nucleic Acid and Protein Delivery: A Combined Strategy with Membrane-Lytic Peptides To Facilitate Endosomal Escape
(Hirose, Hisaaki; Akishiba, Misao; Tsuji, Shogo; Imanishi, Miki; Futaki, Shiroh)
Tag: TALE

[Bioconjugate Chem. 2020, 31, 577−583]
Live-Cell Imaging of Protein Degradation Utilizing Designed Protein-Tag Mutant and Fluorescent Probe with Turn-Off Switch
(Gao, Jingchi; Hori, Yuichiro; Takeuchi, Osamu; Kikuchi, Kazuya)
Tag: FP, FL, Sn, POI

[Bioconjugate Chem. 2020, 31, 794−802]
Regioselective Chemical Modification of Cysteine Residues on Protein Surfaces Focusing on Local Environment around the Conjugation Site
(Miyake, Teruyuki; Tamaki, Ryosei; Asanuma, Moeko; Fukada, Yoji; Hirota, Shun; Matsuo, Takashi)
Tag: AK, Cys, FL, C, expt., Pyr, Py

[Bioconjugate Chem. 2020, 31, 803−812]
Noninvasive Early Detection of Calpain 2-Enriched Non-Small Cell Lung Cancer Using a Human Serum Albumin-Bounded Calpain 2 Nanosensor
(Kwon, Seung-Hae; Wi, Taemin; Park, Yong Il; Kim, Min Woo; Lee, Gibok; Higaki, Takumi; Choi, Jung Hoon; Lee, Ruda)
Tag: SCLC, NSCLC, FL, Sn, HSA, SA, expt., NIR, IR

[Bioconjugate Chem. 2020, 31, 821−833]
Development of Cell-Penetration PG-Surfactants and Its Application in External Peptide Delivery to Cytosol
(Sumito, Natsumi; Koeda, Shuhei; Umezawa, Naoki; Inoue, Yasumichi; Tsukiji, Shinya; Higuchi, Tsunehiko; Mizuno, Toshihisa)
Tag: esp., m, MITO, SC, Alk

[Bioconjugate Chem. 2020, 31, 916−922]
Endosomal Escape of Peptide-Photosensitizer Conjugates Is Affected by Amino Acid Sequences near the Photosensitizer
(Miyoshi, Yuichi; Kadono, Maho; Okazaki, Shigetoshi; Nishimura, Ayano; Kitamatsu, Mizuki; Watanabe, Kazunori; Ohtsuki, Takashi)
Tag: PS, CPP, AA, m, Sn, PD, O, NH2, PDT, PCI, sens, 1O2

[J. Mater. Chem. C 2020, 8, 3821−3829]
Bismuth chalcogenide iodides Bi13S18I2 and BiSI: solvothermal synthesis, photoelectric behavior, and photovoltaic performance
(Li, Sen; Xu, Linfeng; Kong, Xingang; Kusunose, Takafumi; Tsurumachi, Noriaki; Feng, Qi)
Tag: Bi