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Preparation, Characterization and Reactivity of a Bis-hypochlorite Adduct of a Chiral Manganese(IV) Salen Complex

Ikuko Araki ,  Kaoru Fukui , and  Hiroshi Fujii *   Department of Chemistry, Graduate School of Humanities and Sciences,  Nara Women’s University , Kitauoyanishi, Nara 630-8506,  Japan Inorg. Chem. ,  2018 ,  57  (4), pp 1685–1688 DOI:  10.1021/acs.inorgchem.7b02661 Publication Date (Web): February 5, 2018 Copyright © 2018 American Chemical Society *E-mail:  fujii@cc.nara-wu.ac.jp . Synopsis A bis-hypochlorite adduct of a manganese(IV) salen complex having a chiral  trans -cyclohexane-1,2-diamine linkage is successfully prepared and characterized by various spectroscopic methods. The manganese(IV) bis-hypochlorite complex is capable of sulfoxidation, epoxidation, chlorination, and hydrogen abstraction reactions. However, the enantioselectivity of this complex is low, which is consistent with the planar conformation of the salen ligand, as suggested by circular dichroism spectroscopy. https://pu...

Catalytic allylic oxidation of internal alkenes to a multifunctional chiral building block

Liela Bayeh, Phong Q. Le & Uttam K. Tambar Nature 547, 196–200 (13 July 2017) doi:10.1038/nature22805 Received 13 December 2016 Accepted 25 April 2017 Published online 21 June 2017 Article tools pdfのurl:  https://www.nature.com/nature/journal/v547/n7662/pdf/nature22805.pdf 日本語の解説記事 http://www.nature.com/nature/journal/v547/n7662/fp/nature22805_ja.html?lang=ja 立体選択的かつ位置選択的な、内部オレフィンの官能基化についての論文が報告されています。コバルト触媒存在条件下、 不斉源をバイノールとして 、スルフォキシアミドが立体選択的に導入されます。合成反応として重要な点は、スルフォキシアミドは立体を保持したまま、種々の官能基へと変換することが可能です。当然、残っているオレフィン部位も様々な変換が可能です。オレフィンの官能基化をしている方は参考になる論文ではないでしょうか。特に、イントロダクションにしっかり目を通し、どのように重要性を説いているか、ぜひ確認してください。

Selective oxidation of aliphatic C–H bonds in alkylphenols by a chemomimetic biocatalytic system

Lei Du a,b,c,1 , Sheng Dong a,b,1 , Xingwang Zhang a,b , Chengying Jiang d,e , Jingfei Chen a,b , Lishan Yao a,b , Xiao Wang f , Xiaobo Wan f , Xi Liu g,h,i , Xinquan Wang g,h,i , Shaohua Huang a,b , Qiu Cui a,b , Yingang Feng a,b,2 , Shuang-Jiang Liu d,e,2 , and Shengying Li a,b,2 a Shandong Provincial Key Laboratory of Synthetic Biology, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, Shandong 266101, China; b Key Laboratory of Biofuels, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, Shandong 266101, China; c University of Chinese Academy of Sciences, Beijing 100049, China; d State Key Laboratory of Microbial Resources, Institute of Microbiology, Chinese Academy of Sciences, Beijing 100101, China; e Environmental Microbiology and Biotechnology Research Center, Institute of Microbiology, Chinese Academy of Sciences, Beijing 100101, China; f Key Laboratory of Bio-based Materials, Qingd...

Site-selective and stereoselective functionalization of unactivated C–H bonds

Kuangbiao Liao, Solymar Negretti, Djamaladdin G. Musaev, John Bacsa & Huw M. L. Davies Emory University, Atlanta, USA. Nature 2016 , 533 , 230 http://www.nature.com/nature/journal/v533/n7602/pdf/nature17651.pdf Abstruct The laboratory synthesis of complex organic molecules relies heavily on the introduction and manipulation of functional groups, such as carbon–oxygen or carbon–halogen bonds; carbon–hydrogen bonds are far less reactive and harder to functionalize selectively. The idea of C–H functionalization, in which C–H bonds are modified at will instead of the functional groups, represents a paradigm shift in the standard logic of organic synthesis. For this approach to be generally useful, effective strategies for site-selective C–H functionalization need to be developed. The most practical solutions to the site-selectivity problem rely on either intramolecular reactions4 or the use of directing groups within the substrate. A challenging, but potenti...

Stereochemical Course of the Reaction Catalyzed by RimO, a Radical SAM Methylthiotransferase

Bradley J. Landgraf † and Squire J. Booker * † ‡ § † Department of Chemistry, ‡ Department of Biochemistry and Molecular Biology, and § The Howard Hughes Medical Institute, The Pennsylvania State University , University Park, Pennsylvania 16802, United States J. Am. Chem. Soc. , Article ASAP DOI: 10.1021/jacs.5b11035 http://pubs.acs.org/doi/abs/10.1021/jacs.5b11035 http://pubs.acs.org/doi/pdf/10.1021/jacs.5b11035 Abstract RimO is a member of the growing radical S-adenosylmethionine (SAM) superfamily of enzymes, which use a reduced [4Fe–4S] cluster to effect reductive cleavage of the 5′ C–S bond of SAM to form a 5′-deoxyadenosyl 5′-radical (5′-dA • ) intermediate. RimO uses this potent oxidant to catalyze the attachment of a methylthio group (−SCH 3 ) to C3 of aspartate 89 of protein S12, one of 21 proteins that compose the 30S subunit of the bacterial ribosome. However, the exact mechanism by which this transformation takes place has remained elusive. H...

Catalytic Enantioselective Functionalization of Unactivated Terminal Alkenes

John R. Coombs and James P. Morken*  [*] J. R. Coombs, Prof. J. P. Morken Department of Chemistry, Boston College, Merkert Research Labs 2609 Beacon St., Chesnut Hill, MA 02467 (USA) E-mail: morken@bc.edu http://onlinelibrary.wiley.com/doi/10.1002/anie.201507151/abstract http://onlinelibrary.wiley.com/doi/10.1002/anie.201507151/epdf Abstract Terminal alkenes are readily available functional groups which appear in α-olefins produced by the chemical industry, and they appear in the products of many contemporary synthetic reactions. While the organic transformations that apply to alkenes are amongst the most studied reactions in all of chemical synthesis, the number of reactions that apply to nonactivated terminal alkenes in a catalytic enantioselective fashion is small in number. This Minireview highlights the cases where stereocontrol in catalytic reactions of 1-alkenes is high enough to be useful for asymmetric synthesis. 1. Introduction 2. H...

Structurally Defined Molecular Hypervalent Iodine Catalysts for Intermolecular Enantioselective Reactions

Dr. Stefan Haubenreisser, Dr. Thorsten H. Wöste, Dr. Claudio Martínez, Prof. Dr. Kazuaki Ishihara, Prof. Dr. Kilian Muñiz DOI:  10.1002/anie.201507180 Authors Affiliation : Institute of Chemical Research of Catalonia (ICIQ) Abstract Molecular structures of the most prominent chiral non-racemic hypervalent iodine(III) reagents to date have been elucidated for the first time. The formation of a chirally induced supramolecular scaffold based on a selective hydrogen-bonding arrangement provides an explanation for the consistently high asymmetric induction with these reagents. As an exploratory example, their scope as chiral catalysts was extended to the enantioselective dioxygenation of alkenes. A series of terminal styrenes are converted into the corresponding vicinal diacetoxylation products under mild conditions and provide the proof of principle for a truly intermolecular asymmetric alkene oxidation under iodine(I/III) catalysis. 超原子価ヨウ素を活性種とする、オレフィンのエナンチオセレクティブなジアセ...