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Bioinspired Manganese and Iron Complexes for Enantioselective Oxidation Reactions: Ligand Design, Catalytic Activity, and Beyond

Wei Sun,* Qiangsheng Sun Cite This:Acc. Chem. Res.2019 Publication Date:July 23, 2019 https://doi.org/10.1021/acs.accounts.9b00285 鉄、マンガン錯体を用いた不斉酸化触媒についてのレビューです。配位子の構造、基質の選び方、参考になりそうです。 うちでもよく使う、ピリジルアミン系配位子が出てきますが、メチレンリンカーへの嵩高い置換基が効果的なようです。 また、スピロ化合物(下図、右上)なんかも不斉酸化のターゲットになるんですね。

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...

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...

Improving the Catalytic Performance of an Artificial Metalloenzyme by Computational Design

Journal of the American Chemical Society by Tillmann Heinisch, Michela Pellizzoni, Marc Dürrenberger, Christine E. Tinberg, Valentin Köhler, Juliane Klehr, Daniel Häussinger, David Baker and Thomas R. Ward  /  7h  //  keep unread  //  hide  //  preview http://pubs.acs.org/doi/pdf/10.1021/jacs.5b06622   Journal of the American Chemical Society DOI: 10.1021/jacs.5b06622 Visit Website

Catalytic asymmetric hydroamination of unactivated internal olefins to aliphatic amines

Yang Yang, 1 * Shi-Liang Shi, 1 * Dawen Niu, 1 Peng Liu, 2 Stephen L. Buchwald 1 † Catalytic assembly of enantiopure aliphatic amines from abundant and readily available precursors has long been recognized as a paramount challenge in synthetic chemistry. Here, we describe a mild and general copper-catalyzed hydroamination that effectively converts unactivated internal olefins — an important yet unexploited class of abundant feedstock chemicals — into highly enantioenriched a -branched amines ( ≥ 96% enantiomeric excess) featuring two minimally differentiated aliphatic substituents. This method provides a powerful means to access a broad range of advanced, highly functionalized enantioenriched amines of interest in pharmaceutical research and other areas.  1 Depart ment of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.  2 Department of Chemis...

Synergistic Stereocontrol in the Enantioselective Ruthenium-Catalyzed Sulfoxidation of Spirodithiolane-Indolones

Dr. Fangrui Zhong, Dr. Alexander Pöthig and Prof. Dr. Thorsten Bach* Article first published online: 10 JUN 2015 Department Chemie and Catalysis Research Center (CRC), Technische Universität München, Lichtenbergstr. 4, 85747 Garching DOI: 10.1002/chem.201501780 View Full Article with Supporting Information (HTML)   Enhanced Article (HTML)   Get PDF (421K) Abstract A chiral ruthenium catalyst was developed for the enantioselective sulfoxidation of the title compounds. The catalyst combines two elements of chirality, a chiral pybox ligand and a chiral bicylic lactam unit, to which the ligand is attached. The latter unit was shown to improve significantly the performance of the catalyst by exposing one of the two enantiotopic sulfur atoms to the active site via hydrogen-bond mediated coordination. Ten differently substituted substrates were converted into the respective sulfoxides in yields of 52–71 % and with ≥90 % ee. 酸化剤は、PhI(OPiv)2、 or  クメンヒドロペルオキシ...