雑誌会（191204）回答

雑誌会（191204）回答_境田

Catallytically Relevant Intermediates in the Ni-Catalyzed C(sp²)－H and C(sp³)－H Functionalization of Aminoquinoline Substrates.

Pronay Roy, James R. Bour, Jeff W. Kampf, and Melanie S. Sanford

DOI: 10.1021/jacs.9b09109

J. Am. Chem. Soc. ASAP

Q1. Niを用いたCーHヨウ素化反応におけるヨウ素分子の役割

　本論文の中で紹介した、CーHヨウ素化反応において、加えられているヨウ素は、経由する有機金属錯体の中心金属である、ニッケルへのヨウ素原子供与剤であるのと同時に、ニッケル中心への酸化的付加を引き起こす、酸化剤としての役割を果たしている。

Q2. C(sp²)－Ni結合をもつNi錯体(2a)の合成法について誰の文献を引用しているか。

　無水物とイミドがニッケル0価に酸化的付加するという知見は下に示す、参考文献1によって得られ、続く、脱カルボニル化反応によるニッケル2価錯体の形成は以下の参考文献2によって、得られている。

参考文献

1. Zhang, Y.; Rovis, T. J. Chem. Soc., 2004, 126, 15964–15965.

2. Castano, A, M.; Enchavarren, A, M. Organometallics, 1994, 13, 2262–2268.

Q3. C(sp²)－Ni結合をもつニッケル錯体と異なり、C(sp³)－Ni結合をもつニッケル錯体を基質として用いて、140℃まで、昇温したとき、分子内でCーN結合形成反応が起こるのか。

　　本論文には詳細な説明は書いていないが、ニッケルと直接結合している炭素に関して、sp³混成軌道をとっているとき、ｓ軌道の成分が25 %であり、sp²混成軌道のそれよりも小さいことから、より、結合が外れやすく、ヨウ素分子の酸化的付加よりも早く、分子内のCーN形成反応が進行し、ラクタムを生成すると考えられる。

Q4. Ni(lll)錯体の結晶構造を決めている論文は他にあるか。

　今回の論文のほかにニッケル3価錯体の結晶構造を決めたものにこのようなものがある。

1. T. Fogeron, T. K. Todorova, J-P. Porcher, M. Gomez-Mingot, L-M. Chamoreau, C. Mellot-Draznieks, Y. Li, M. Fontecave. ACS Catal. 2018, 8, 2030−2038.

2. R. Kunert, C. Philouze, O. Jarjayes, F. Thomas. Inorg. Chem. 2019, 58, 8030−8044.

Electrochemical evidence that pyranopterin redox chemistry controls the catalysis of YedY, a mononuclear Mo enzyme

Hope Adamson a, Alexandr N. Simonov b, Michelina Kierzek c, Richard A. Rothery c, Joel H. Weiner c, Alan M. Bond b, and Alison Parkin a,1 a Department of Chemistry, University of York, Heslington, York YO10 5DD, United Kingdom; b School of Chemistry, Monash University, Clayton, VIC 3800, Australia; and c Department of Biochemistry, University of Alberta, Edmonton, AB T6G 2H7, Canada Edited by Harry B. Gray, California Institute of Technology, Pasadena, CA, and approved October 13, 2015 (received for review August 25, 2015) http://www.pnas.org/content/112/47/14506.short A long-standing contradiction in the field of mononuclear Mo enzyme research is that small-molecule chemistry on active-site mimic compounds predicts ligand participation in the electron transfer reactions, but biochemical measurements only suggest metal-centered catalytic electron transfer.With the simultaneous measurement of substrate turnover and reversible electron transfer that is provided by Fourier-...

Rhenium(V)–oxo corrolazines: isolating redox-active ligand reactivity

Jan Paulo T. Zaragoza,a Maxime A. Sieglera and David P. Goldberg* Chem. Commun., 2015, Advance Article DOI: 10.1039/C5CC07956J Received 22 Sep 2015, Accepted 15 Oct 2015 First published online 28 Oct 2015 http://pubs.rsc.org/en/content/articlelanding/2015/cc/c5cc07956j#!divAbstract Abstract The synthesis of the first example of a third-row metallocorrolazine characterized by single crystal X-ray diffraction is reported. This ReV(O) porphyrinoid complex shows an exclusively ligand-based reactivity with strong acids and oxidizing agents. The one-electron oxidized π-radical-cation complex is capable of H-atom abstraction.

Tuning Reactivity and Selectivity in Hydrogen Atom Transfer from Aliphatic C–H Bonds to Alkoxyl Radicals: Role of Structural and Medium Effects

Michela Salamone and Massimo Bietti* Dipartimento di Scienze e Tecnologie Chimiche, Università “Tor Vergata”, Via della Ricerca Scientifica, Italy Acc. Chem. Res., Article ASAP DOI: 10.1021/acs.accounts.5b00348 Publication Date (Web): November 6, 2015 クメンパーオキシドを光で開裂させることにより、生成するクミルアルコキシルラジカルによるアルカンやアミンのC–H切断の速度定数などの情報がまとまっています。溶媒や、酸、基質の形が反応速度定数に与える影響を定量的に評価しています。酸化反応をしている方は、手元に置いておいても良いのでしょうか。

C–H Bond Oxidation Catalyzed by an Imine-Based Iron Complex: A Mechanistic Insight

Giorgio Olivo§¶, Martina Nardi§, Diego Vìdal¶, Alessia Barbieri§, Andrea Lapi§‡, Laura Gómez¶⊥, Osvaldo Lanzalunga§‡, Miquel Costas*¶, and Stefano Di Stefano*§‡ § Università degli Studi di Roma, Rome, Italy ¶ Institut de Química Computacional i Catàlisi (IQCC), Girona, Spain Inorg. Chem., 2015, 54 (21), pp 10141–10152 DOI: 10.1021/acs.inorgchem.5b01500 Publication Date (Web): October 12, 2015 A family of imine-based nonheme iron(II) complexes (LX)2Fe(OTf)2 has been prepared, characterized, and employed as C–H oxidation catalysts. Ligands LX (X = 1, 2, 3, and 4) stand for tridentate imine ligands resulting from spontaneous condensation of 2-pycolyl-amine and 4-substituted-2-picolyl aldehydes. Fast and quantitative formation of the complex occurs just upon mixing aldehyde, amine, and Fe(OTf)2 in a 2:2:1 ratio in acetonitrile solution. The solid-state structures of (L1)2Fe(OTf)(ClO4) and (L3)2Fe(OTf)2 are reported, showing a low-spin octahedral iron center, with the lig...

Oxidative Alkene Cleavage Catalysed by Manganese-Dependent Cupin TM1459 from Thermotoga maritima

van Hajnal 1 , Kurt Faber 1,2 , Helmut Schwab 1,3 , Mélanie Hall 2,* and Kerstin Steiner 1,* a acib, Austrian Centre of Industrial Biotechnology GmbH, Petersgasse 14, 8010 Graz, Austria Fax: ( + 43)-316-873-9302; phone: ( + 43)-316-873-9346; e-mail: kerstin.steiner@acib.at b Department of Chemistry, University of Graz, Heinrichstraße 28, 8010 Graz, Austria Fax: ( + 43)-316-380-9840; phone: ( + 43)-316-380-5479; e-mail: melanie.hall@uni-graz.at c Institute of Molecular Biotechnology, TU Graz, Petersgasse 14, 8010 Graz, Austria Adv .S ynth. Catal. 2015 , 357 , 3 309 –3 316 DOI: 10.1002/adsc.201500608 Abstract A novel biocatalytic oxidative alkene cleavage activity was identified in protein TM1459 from Thermotoga maritima , a so far uncharacterised metalloprotein with a cupin fold, which preferentially binds manganese (over iron and zinc). Various styrene derivat...

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