Article Previous Article Next Article Articles ASAP Reactivity of a Cobalt(III)–Hydroperoxo Complex in Electrophilic Reactions Bongki Shin † , Kyle D. Sutherlin ‡ , Takehiro Ohta § , Takashi Ogura § , Edward I. Solomon * ‡ ∥ , and Jaeheung Cho * † † Department of Emerging Materials Science, DGIST , Daegu 42988, Korea ‡ Department of Chemistry, Stanford University , Stanford, California 94305, United States § Picobiology Institute, Graduate School of Life Science, University of Hyogo , RSC-UH LP Center, Hyogo 679-5148, Japan ∥ Stanford Synchrotron Radiation Laboratory, Stanford Linear Accelerator Center , Menlo Park, California 94025, United States Inorg. Chem. , Article ASAP DOI: 10.1021/acs.inorgchem.6b02288 Publication Date (Web): November 15, 2016 Copyright © 2016 American Chemical ...
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Ambika Bhagi-Damodaran 1 , Matthew A. Michael 2 , Qianhong Zhu 3 , Julian Reed 4 , Braddock A. Sandoval 1 , Evan N. Mirts 5 , Saumen Chakraborty 1 , Pierre Moënne-Loccoz 3 * , Yong Zhang 2 * and Yi Lu 1,4,5 * Nature Chemistry (2016) doi:10.1038/nchem.2643 Received 05 April 2016 Accepted 09 September 2016 Published online 07 November 2016 http://www.nature.com/nchem/journal/vaop/ncurrent/pdf/nchem.2643.pdf Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois, USA. 2 Department of Biomedical Engineering, Chemistry, and Biological Sciences, Stevens Institute of Technology, Hoboken, New Jersey, USA. 3 Division of Environmental & Biomolecular Systems, Institute o...
Teresa Corona, Lídia Ribas, Mireia Rovira, Dr. Erik R. Farquhar, Dr. Xavi Ribas , Prof. Dr. Kallol Ray , Dr. Anna Company First published: 10 October 2016 Full publication history DOI: 10.1002/anie.201607238 View/save citation http://onlinelibrary.wiley.com/doi/10.1002/anie.201607238/full Abstract High-valent terminal copper–nitrene species have been postulated as key intermediates in copper-catalyzed aziridination and amination reactions. The high reactivity of these intermediates has prevented their characterization for decades, thereby making the mechanisms ambiguous. Very recently, the Lewis acid adduct of a copper–nitrene intermediate was trapped at −90 °C and shown to be active in various oxidation reactions. Herein, we describe for the first time the synthesis and spectroscopic characterization of a terminal copper(II)–nitrene radical specie...
Highly EnantioselectiveIron-Catalyzed cis-Dihydroxylation ofAlkenes with Hydrogen Peroxide Oxidant via an FeIII-OOH ReactiveIntermediate
Chao Zang + , Yungen Liu + , Zhen-Jiang Xu, Chun-Wai Tse, Xiangguo Guan, Jinhu Wei, Jie- Sheng Huang, and Chi-Ming Che* [*] Dr. C. Zang, [+] Dr. Z.-J. Xu, Prof. Dr. C.-M. Che Shanghai–Hong Kong Joint Laboratory in Chemical Synthesis Shanghai Institute of Organic Chemistry 354 Feng Lin Road, Shanghai (China) E-mail: cmche@hku.hk Dr. Y. Liu, [+] C.-W. Tse, Dr. X. Guan, J. Wei, Dr. J.-S. Huang, Prof. Dr. C.-M. Che Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The University of Hong Kong Pokfulam Road, Hong Kong (China) [ + ] These authors contributed equally to this work. http://onlinelibrary.wiley.com/doi/10.1002/anie.201603410/abstract Abstract The development of environmentally benign cata- lysts for highly enantioselective asymmetric cis-dihydroxyla- tion (AD) of alkenes with broad substrate scope remains a challenge. By employing [Fe II (L)(OTf) 2 ] (L = N,N ’ - dimethyl-N,N ’ -bis(2-methyl-8-quinolyl)-cyclohexane-1...
A Ruthenium(III)–Oxyl Complex Bearing Strong Radical Character Yoshihiro Shimoyama, Tomoya Ishizuka, Hiroaki Kotani, Yoshihito Shiota, Kazunari Yoshizawa, Kaoru Mieda, Takashi Ogura, Toshihiro Okajima, Shunsuke Nozawa, and Takahiko Kojima* Abstract Proton-coupled electron-transfer oxidation of a RuII OH2 complex, having an N-heterocyclic carbene ligand, gives a RuIII OC species, which has an electronically equivalent structure of the RuIV=O species, in an acidic aqueous solution. The RuIII OC complex was characterized by spectroscopic methods and DFT calculations. The oxidation state of the Ru center was shown to be close to +3; the Ru O bond showed a lower-energy Raman scattering at 732 cm 1 and the Ru O bond length was estimated to be 1.77(1) . The RuIII OC complex exhibits high reactivity in substrate oxidation under catalytic conditions; particularly, benzaldehyde and the derivatives are oxidized to the corresponding benzoic acid through C H abstraction from the formyl g...