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Photo‐biocatalytic One‐Pot Cascades for the Enantioselective Synthesis of 1,3‐Mercaptoalkanol Volatile Sulfur Compounds
10.1002/anie.201802135 2018-04-14 The synthesis of enantiomerically pure 1,3‐mercaptoalkanol volatile sulfur compounds through a one‐pot photo‐biocatalytic cascade reaction is described. Two new KRED biocatalysts with opposite enantioselectivity were discovered and proved to be efficient on a... |
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Synthesis of (bis)Silicon Complexes of [38], [37], and [36]Octaphyrins: Aromaticity Switch and Stable Radical Cation
10.1002/anie.201801986 2018-04-14 Silicon complexation of a [38]octaphyrin (1) was accomplished by reaction with an excess amount of MeSiCl3 in the presence of N,N‐diisopropylethylamine, thus giving an aromatic [38]octaphyrin bis(silicon) complex 2. This complex was interconvertible with an a... |
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Samarium Polystibides Derived from Highly Activated Nanoscale Antimony
10.1002/anie.201802250 2018-04-14 Zintl ions in molecular compounds are of fundamental interest for basic research and application. Two reactive antimony sources are presented that allow direct access to molecular polystibide compounds. These are Sb amalgam (Sb/Hg) and ultrasmall Sb0 nanopart... |
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A Monoaryllead Trichloride that Resists Reductive Elimination
10.1002/anie.201712944 2018-04-14 Transmetallation of Pb(OAc)4 with R2Hg (1), followed by treatment with HCl in Et2O, provided RPbCl3 (2), the first kinetically stabilized monoorganolead trihalide that resists reductive elimination under ambient conditions. The kinetic stabilisation relies on... |
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On the Origin of the Distinctly Different Reactivity of Ruthenium in [MO]+/CH4 Systems (M=Fe, Ru, Os)
10.1002/anie.201800173 2018-04-14 The thermal gas‐phase reactions of [RuO]+ with methane have been explored by FT‐ICR mass spectrometry and high‐level quantum‐chemical calculations. In contrast to the previously studied [FeO]+/CH4 and [OsO]+/CH4 couples, which undergo oxygen/hydrogen atom tra... |
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Natural Product Diversification Mediated by Alternative Transcriptional Starting
10.1002/anie.201713199 2018-04-14 Photorhabdus luminescens dedicates a significant proportion of its genome to the production of natural products. These products and the structural variation in their derivatives may occur by a number of well‐described mechanisms, such as module skipping or pr... |
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CO2 Binding and Splitting by Boron–Boron Multiple Bonds
10.1002/anie.201802117 2018-04-14 The room‐temperature, ambient‐pressure reactions of CO2 with two species containing boron–boron multiple bonds led to the incorporation of either one or two CO2 molecules. The structural characterization of a thermally unstable intermediate in one case indica... |
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2‐Hydroxybenzophenone as a Chemical Auxiliary for the Activation of Ketiminoesters for Highly Enantioselective Addition to Nitroalkenes under Bifunctional Catalysis
10.1002/anie.201800435 2018-04-14 An organocatalytic system is presented for the Michael addition of monoactivated glycine ketimine ylides with a bifunctional catalyst. The ketimine bears an ortho hydroxy group, which increases the acidity of the methylene hydrogen atoms and enhances the reac... |
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Synthesis of an Iron(IV) Aqua–Oxido Complex Using Ozone as an Oxidant
10.1002/anie.201800475 2018-04-11 The iron(IV) oxido complex [(tmc)Fe=O(OTf)]OTf with the macrocyclic ligand 1,4,8,11‐tetramethyl‐1,4,8,11‐tetraazacyclo‐tetradecane (tmc) has been synthesized using ozone as an oxidant. By adding water to this compound the complex [(H2O)(tmc)Fe=O)](OTf)2 could... |
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Asymmetric [3+2] Photocycloadditions of Cyclopropanes with Alkenes or Alkynes through Visible‐Light Excitation of Catalyst‐Bound Substrates
10.1002/anie.201802316 2018-04-10 The herein reported visible‐light‐activated catalytic asymmetric [3+2] photocycloadditions between cyclopropanes and alkenes or alkynes provide access to chiral cyclopentanes and cyclopentenes, respectively, in 63–99 % yields and with excellent enantioselecti... |