[読みたい論文] シリレノイドとエンインのダブル環化反応

Viewed: 03:11:31 in December 11, 2019

Posted: March 22, 2019

[Org. Lett. 2019, 21 (6), 1649−1653] Alkene Catalytic Generation of Rhodium Silylenoid for Alkene−Alkyne−Silylene [2 + 2 + 1] Cycloaddition (Ohmura, Toshimichi; Sasaki, Ikuo; Suginome, Michinori)

Keywords: Rh; cod; dppm; BPin

ロジウム触媒によるエンイン化合物とシリレン等価体のダブル環化反応に関する研究のようです。シリレン等価体は表題の構造の化合物。


反応機構が気になるので、読みたい論文に追加です。シリレン等価体が反応に関与するところ、フリーのシリレンの反応とどう違うのか、ですね。

それと気になるのが反応の立体選択性です。R4とR5の向きも気になりますが、もっと気になるのがR2とR3の向きです。Supporting informationを見る限り、前者は出発の化合物の二重結合の幾何異性がきっちり反映されている一方、後者については「1:1のジアステレオマー混合物」の模様。これらの実験結果に付いて、論文本体でどのような記述がなされているのか、気になるところです。

基質の合成法も見どころの一つです。

この記事を書いた人
「牧岡ふうふ堂」オーナー。博士(工学)。
酒都圏在住。
某地方の国立系工業大学でアシスタントをしていました。 専門は有機反応・金属錯体(主に希土類)・π共役系。
twitterアカウントは@makiokafufudo(お仕事用)、@ymakioka(個人用)です。

 

1947年はこんな年

人名反応など
Cook−Heilbronチアゾール合成 [Doi 1]
ノーベル化学賞
アルカロイドの研究
(Sir Robert Robinson)
できごと
贈与税新設
国際標準化機構(ISO)設立
国際通貨基金(IMF)操業開始
日本国憲法施行
最高裁判所発足
労働省発足
国家公務員法公布
公正取引委員会設置
学校給食開始
玉川大学開校
浦上糧食工業所(ハウス食品)設立
労働基準法公布・施行
日本教職員組合(日教組)結成
学校教育法施行(六三三学制)
新宝島(手塚治虫)出版。
「立春に卵が立つ」と話題に
東京ラグビー場(秩父宮ラグビー場)完成
利根川が決壊

 

きょうのどうぶつ

ここの画像を使用しています。

近所の水源地の側溝にいたアカミミ。

 

あわせてどうぞ

SOHOのすすめ記事一覧 2019年
お仕事関係の記事のリストです(2019年)。

読みたい論文シリーズ − 2019年1Q
読みたいけと読んでいない論文を、構造式を描きながら紹介します(2019年1〜3月)。

 

[読みたい論文] アルカリ土類金属触媒による水素移動反応
アルケンと1,4-シクロヘキサジエンの反応です。
Angew. Chem. Int. Ed. 2019, 58 (13), 4248−4253.

[読みたい論文] ホスフィンで安定化させたジハロジボレン
ホウ素−ホウ素二重結合を持つ化合物。
Angew. Chem. Int. Ed. 2019, 58 (13), 4405−4409.

[読みたい論文] バナジウムイミド触媒によるピロール合成
アルキンとアゾベンゼンから。
J. Am. Chem. Soc. 2019, 141 (10), 4194−4198.

[読みたい論文] まだまだ拡がるHiyamaカップリング
著者に注目。
Chem. Lett. 2019, 48 (4), 361−363.

[読みたい論文] 光学活性亜鉛触媒によるエナンチオ選択的分子内Conia-ene型反応
Conia-ene"型"反応です。
J. Am. Chem. Soc. 2019, 141 (10), 4199−4203.

[読みたい論文] ハロゲン化アリールのハロゲン/サマリウム交換: ハロゲン/マグネシウム交換よりも100万倍近く速い
有機亜鉛の大家の報告です。
Angew. Chem. Int. Ed. 2019, 58 (12), 4046−4050.

[読みたい論文] マグネシウム/クロロシラン還元剤を使う不飽和エステルのトリフルオロアセチル化
継続は力なり、です。
Asian J. Org. Chem. 2019, 8 (3), 344−347.

[読みたい論文] ラジカル反応らしくないC(sp3)−H結合活性化反応
銅触媒の反応場をうまく制御しています。
Angew. Chem. Int. Ed. 2019, 58 (11), 3421−3425.

[読みたい論文] 室温で進行するカルボニル炭素のgem-ジフルオロ化反応
フッ素源が多い反応です。
Org. Lett. 2019, 21 (5), 1350−1353.

[読みたい論文] ピナコールシラン: 金属触媒不要の還元反応
ルイス塩基は必要のようです。
Org. Lett. 2019, 21 (5), 1402−1406.

 

注目の論文

[ACS Omega 20190321072756, 2019, 3−5540]
Expression, Purification, and Characterization of Human Diacylglycerol Kinase Î
(Saito, Takumi; Takahashi, Daisuke; Sakane, Fumio)
Tag: DAGK, DAG, SBDD, Cat, ADO, PA, PS, DGK, CD, M, ATP

[ACS Omega 20190321072810, 2019, 3−5517]
Glycosaminoglycan-Conjugated Insulin Derivatives Suitable for Once-Daily Formulations
(Fukushima, Masanobu; Hirayama, Tetsuya; Ichikawa, Megumi; Kitazawa, Ikue; Kojima, Kazuhiro; Sakai, Tokiko; Takatsu, Yoshihiro; Ohtaki, Tetsuya)
Tag: Ch, STZ, GAG, Glu, INS, Glc, GU, Glu, Glu

CO2還元  
[ACS Omega 20190321072825, 2019, 3−5451]
Photocatalytic Activity of Ga2O3 Supported on Al2O3 for Water Splitting and CO2 Reduction
(Ito, Ryota; Akatsuka, Masato; Ozawa, Akiyo; Kato, Yuma; Kawaguchi, Yu; Yamamoto, Muneaki; Tanabe, Tetsuo; Yoshida, Tomoko)
Tag: CO2R, C

[ACS Appl. Mater. Interfaces 20190321073819, 2019, 11−10785]
Eco-Friendly Push-Coated Polymer Solar Cells with No Active Material Wastes Yield Power Conversion Efficiencies over 5.5%
(Inaba, Shusei; Arai, Ryosuke; Mihai, Geanina; Lazar, Oana; Moise, Calin; Enachescu, Marius; Takeoka, Yuko; Vohra, Varun)
Tag: ST, P3HT, PSC, PV, LBG, 107-92-6, PCE, cbz, iPSC, Me, Ph, e-, TF, SC, PDMS, AVT

高分子電解質  
[ACS Appl. Mater. Interfaces 20190321073933, 2019, 11−10841]
Designing Responsive Photonic Crystal Patterns by Using Laser Engraving
(Yue, Youfeng; Kurokawa, Takayuki)
Tag: NS, PBG, PC, PhC, PEL, RPC

カーボンナノチューブ  
[ACS Appl. Mater. Interfaces 2019032107404, 2019, 11−10862]
Controllable Preparation of Ordered and Hierarchically Buckled Structures for Inflatable Tumor Ablation, Volumetric Strain Sensor, and Communication via Inflatable Antenna
(Wang, Run; Liu, Zhongsheng; Wan, Guoyun; Jia, Tianjiao; Zhang, Chao; Wang, Xuemin; Zhang, Mei; Qian, Dong; de Andrade, Monica Jung; Jiang, Nan; Yin, Shougen; Zhang, Rui; Feng, Deqiang; Wang, Weichao; Zhang, Hui; Chen, Hong; Wang, Yinsong; Ovalle-Robles, Raquel; Inoue, Kanzan; Lu, Hongbing; Fang, Shaoli; Baughman, Ray H.; Liu, Zunfeng)
Tag: RF, NT, C, CNT

環化付加反応  
[Tetrahedron Lett. 20190321074610, 2019, 14−975]
Synthesis of bridgehead-functionalized triptycene quinones via Lewis acid–promoted Diels-Alder reaction of 9-acyloxyanthracenes
(Matsumoto, Kenji; Nakano, Rina; Hirokane, Tsukasa; Yoshida, Masahiro)
Tag: BQ, DA, NQ, TPC, CA

[Tetrahedron Lett. 20190321074625, 2019, 14−1001]
Atom-economical brominations with tribromide complexes in the presence of oxidants
(Yubata, Kotaro; Matsubara, Hiroshi)
Tag: Br

[Tetrahedron 20190321075010, 2019, 14−2239]
Eremophilane, bakkane, secoeremophilane, and secobakkane sesquiterpenoids from Ligularia virgaurea collected in China
(Saito, Yoshinori; Iga, Saori; Hoshiyama, Kie; Nakashima, Katsuyuki; Okamoto, Yasuko; Kuroda, Chiaki; Gong, Xun; Tori, Motoo)

液晶  
[J. Organomet. Chem. 20190321075648, 2019, −34]
Design and phase transition behavior of siloxane-based monomeric and dimeric liquid crystals bearing cholesteryl mesogenic groups
(Katsuki, Kaito; Kaneko, Kosuke; Kaneko, Kimiyoshi; Kato, Riki; Miyamoto, Nobuyoshi; Hanasaki, Tomonori)
Tag: BP, Alk, XR, OM, Chol, POM, DSC, LC, XRD, M

[Angew. Chem. Int. Ed. 20190321080510, 2019, 14−4705]
Dynamic Kinetic Resolution of Aldehydes by Hydroacylation
(Chen, Zhiwei; Aota, Yusuke; Nguyen, Hillary M. H.; Dong, Vy M.)
Tag: DKR, NH2, KR, CPon, CP, Rh, C

[Angew. Chem. Int. Ed. 20190321081149, 2019, 14−4526]
Development of α-Gal–Antibody Conjugates to Increase Immune Response by Recruiting Natural Antibodies
(Sianturi, Julinton; Manabe, Yoshiyuki; Li, Hao-Sheng; Chiu, Li-Ting; Chang, Tsung-Che; Tokunaga, Kento; Kabayama, Kazuya; Tanemura, Masahiro; Takamatsu, Shinji; Miyoshi, Eiji; Hung, Shang-Cheng; Fukase, Koichi)
Tag: Ab

[Angew. Chem. Int. Ed. 20190321081327, 2019, 14−4454]
Towards the Evolution of Artificial Metalloenzymes—A Protein Engineer's Perspective
(Markel, Ulrich; Sauer, Daniel F.; Schiffels, Johannes; Okuda, Jun; Schwaneberg, Ulrich)
Tag: HTS, HT, C

[Angew. Chem. Int. Ed. 2019032108153, 2019, 13−4381]
Approach to Fully Substituted Cyclic Nitrones from N-Hydroxylactam Derivatives: Development and Application to the Total Synthesis of Cylindricine?C
(Hiraoka, Shobu; Matsumoto, Tsutomu; Matsuzaka, Koki; Sato, Takaaki; Chida, Noritaka)
Tag: Nu

[Angew. Chem. Int. Ed. 20190321081520, 2019, 13−4371]
A Tetrasilicon Analogue of Bicyclo[1.1.0]but-1(3)-ene Containing a Si=Si Double Bond with an Inverted Geometry
(Iwamoto, Takeaki; Abe, Takashi; Sugimoto, Kunihisa; Hashizume, Daisuke; Matsui, Hiroshi; Kishi, Ryohei; Nakano, Masayoshi; Ishida, Shintaro)
Tag: C, Si, DB, ABS, CTC

自己集合 鉄  
[Angew. Chem. Int. Ed. 20190321081635, 2019, 13−4339]
Structure Switching and Modulation of the Magnetic Properties in Diarylethene-Bridged Metallosupramolecular Compounds by Controlled Coordination-Driven Self-Assembly
(Li, Zhao-Yang; Dai, Jing-Wei; DamjanoviÄ?, Marko; Shiga, Takuya; Wang, Jin-Hua; Zhao, Jia; Oshio, Hiroki; Yamashita, Masahiro; Bu, Xian-He)
Tag: SCO, SC, Fe, DAE, SA, CDSA

パラジウム  
[Angew. Chem. Int. Ed. 2019032108182, 2019, 13−4297]
Palladium-Catalyzed Construction of Quaternary Stereocenters by Enantioselective Arylation of Î-Lactams with Aryl Chlorides and Bromides
(Jette, Carina I.; Geibel, Irina; Bachman, Shoshana; Hayashi, Masaki; Sakurai, Shunya; Shimizu, Hideki; Morgan, Jeremy B.; Stoltz, Brian M.)
Tag: Pd, E, El, Ar, e-

[Angew. Chem. Int. Ed. 20190321081916, 2019, 13−4264]
Total Synthesis of Actinorhodin
(Ninomiya, Mamiko; Ando, Yoshio; Kudo, Fumitaka; Ohmori, Ken; Suzuki, Keisuke)
Tag: SC, M

[Angew. Chem. Int. Ed. 2019032108239, 2019, 13−4169]
Selective Ion Exchange in Supramolecular Channels in the Crystalline State
(Ichihashi, Katsuya; Konno, Daisuke; Maryunina, Kseniya Yu.; Inoue, Katsuya; Toyoda, Kazuhiro; Kawaguchi, Shogo; Kubota, Yoshiki; Tatewaki, Yoko; Akutagawa, Tomoyuki; Nakamura, Takayoshi; Nishihara, Sadafumi)
Tag: IX, SC

自己集合  
[ChemPhysChem 2019032108240, 2019, 6−898]
Long-Range Lateral Correlation between Self-Assembled Domains of Fluorocarbon-Hydrocarbon Tetrablocks by Quantitative GISAXS
(Abuillan, Wasim; Veschgini, Mariam; Mielke, SalomÃ; Yamamoto, Akihisa; Liu, Xianhe; Konovalov, Oleg; Krafft, Marie Pierre; Tanaka, Motomu)
Tag: NN, VdW, HC, GI, GISAX, GISAXS, AWI, SA

[ChemElectroChem 20190321083237, 2019, 6−1683]
Increasing the Electric Double-Layer Capacitance in Boron-Doped Diamond Electrodes
(Takagi, Kazuaki; Natsui, Keisuke; Watanabe, Takeshi; Einaga, Yasuaki)
Tag: BDD, EDL, B, C, EC, BDDE, DLC

鉄  
[J Comput Chem 2019032108393, 2019, 12−1248]
Reduction potential calculations of the Fe–S clusters in Thermus thermophilus respiratory complex I
(Tran, Kelly N.; Niu, Shuqiang; Ichiye, Toshiko)
Tag: PB, Fe, ET, S, DFT, SC, e-

膜タンパク質 量子ドット  
[Chem. Eur. J. 20190321084450, 2019, 16−4047]
Diselenolane-Mediated Cellular Uptake: Efficient Cytosolic Delivery of Probes, Peptides, Proteins, Artificial Metalloenzymes and Protein-Coated Quantum Dots
(Bartolami, Eline; Basagiannis, Dimitris; Zong, Lili; Martinent, RÃmi; Okamoto, Yasunori; Laurent, Quentin; Ward, Thomas R.; Gonzalez-Gaitan, Marcos; Sakai, Naomi; Matile, Stefan)
Tag: Se, MP, QD, OTW

[Polym. Chem. 20190321084639, 2019, 12−1508]
Construction of polyporous polymer microspheres with a tailored mesoporous wall
(Weng, Hanqin; Wu, Zhihao; Zhao, Chi; Wang, Mozhen; Ge, Xuewu; Yamashita, Shinichi; Tang, Jia; Lin, Mingzhang)

[Chem. Commun. 20190321084917, 2019, 24−3556]
A facile preparation of functional cycloalkynes via an azide-to-cycloalkyne switching approach
(Yoshida, Suguru; Kuribara, Tomoko; Ito, Harumi; Meguro, Tomohiro; Nishiyama, Yoshitake; Karaki, Fumika; Hatakeyama, Yasutomo; Koike, Yuka; Kii, Isao; Hosoya, Takamitsu)
Tag: Cu

配位高分子  
[CrystEngComm 20190321085832, 2019, 12−1886]
Versatile coordination architectures of products generated by the in situ reaction of a doubly bis(2-pyridyl)pyrazolate bridged dinuclear copper(ii) complex with tetracyanoethylene
(Ishikawa, Ryuta; Ueno, Shunya; Hamatake, Yumi; Horii, Yoji; Miyazaki, Yuji; Nakano, Motohiro; Noda, Takeshi; Uematsu, Mikoto; Kawata, Satoshi)
Tag: TCNE, VT, pc, IR, EPR, ESR, SP, SPy, SPl, XR, SCXRD, THF, CP, CW, XRD, e-, SC

[J. Mater. Chem. A 20190321090032, 2019, 12−7232]
Thermodynamic maximum of Y doping level in barium zirconate in co-sintering with NiO
(Ueno, Katsuhiro; Hatada, Naoyuki; Han, Donglin; Uda, Tetsuya)
Tag: Ni, Ba, FC, C

ナノ粒子  
[J. Mater. Chem. A 20190321090046, 2019, 12−7221]
Hollow titanosilicate nanospheres encapsulating PdAu alloy nanoparticles as reusable high-performance catalysts for a H2O2-mediated one-pot oxidation reaction
(Kuwahara, Yasutaka; Matsumura, Ryo; Yamashita, Hiromi)
Tag: Cat, NP, C

[Dalton Trans. 20190321091517, 2019, 12−3973]
Subunit–subunit interactions play a key role in the heme-degradation reaction of HutZ from Vibrio cholerae
(Uchida, Takeshi; Ota, Kazuki; Sekine, Yukari; Dojun, Nobuhiko; Ishimori, Koichiro)
Tag: RE, RR, FL, O, His, H, ET, V, Val, VC, AA, RET, e-

[Dalton Trans. 20190321091847, 2019, 12−3840]
Methoxy-substituted tetrakisquinoline analogs of EGTA and BAPTA for fluorescence detection of Cd2+?
(Mikata, Yuji; Kaneda, Minori; Konno, Hideo; Matsumoto, Arimasa; Sato, Shin-ichiro; Kawamura, Masaya; Iwatsuki, Satoshi)
Tag: FL, N, O, FLD, FE, EG, 91-22-5, C2H4