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Mark M. Maturi Matthias Wenninger Dr. Rafael Alonso Dr. Andreas Bauer Dr. Alexander Pöthig Prof. Dr. Eberhard Riedle Prof. Dr. Thorsten Bach 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(23):7461-7472
The intramolecular [2+2] photocycloaddition of four 4‐(but‐3‐enyl)oxyquinolones (substitution pattern at the terminal alkene carbon atom: CH2, Z‐CHEt, E‐CHEt, CMe2) and two 3‐(but‐3‐enyl)oxyquinolones (substitution pattern: CH2, CMe2) was studied. Upon direct irradiation at λ=300 nm, the respective cyclobutane products were formed in high yields (83–95 %) and for symmetrically substituted substrates with complete diastereoselectivity. Substrates with a Z‐ or E‐substituted terminal double bond showed a stereoconvergent reaction course leading to mixtures of regio‐ and diastereomers with almost identical composition. The mechanistic course of the photocycloaddition was elucidated by transient absorption spectroscopy. A triplet intermediate was detected for the title compounds, which–in contrast to simple alkoxyquinolones such as 3‐butyloxyquinolone and 4‐methoxyquinolone–decayed rapidly (τ≈1 ns) through cyclization to a triplet 1,4‐diradical. The diradical can evolve through two reaction channels, one leading to the photoproduct and the other leading back to the starting material. When the photocycloaddition was performed in the presence of a chiral sensitizer (10 mol %) upon irradiation at λ=366 nm in trifluorotoluene as the solvent, moderate to high enantioselectivities were achieved. The two 3‐(but‐3‐enyl)oxyquinolones gave enantiomeric excesses (ees) of 60 and 64 % at ?25 °C, presumably because a significant racemic background reaction occurred. The 4‐substituted quinolones showed higher enantioselectivities (92–96 % ee at ?25 °C) and, for the terminally Z‐ and E‐substituted substrates, an improved regio‐ and diastereoselectivity. 相似文献
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A Chiral Thioxanthone as an Organocatalyst for Enantioselective [2+2] Photocycloaddition Reactions Induced by Visible Light 下载免费PDF全文
Dr. Rafael Alonso Prof. Dr. Thorsten Bach 《Angewandte Chemie (International ed. in English)》2014,53(17):4368-4371
Thioxanthone 1 , which was synthesized in a concise fashion from methyl thiosalicylate, exhibits a significant absorption in the visible light region. It allows for an efficient enantioselective catalysis of intramolecular [2+2] photocycloaddition reactions presumably by triplet energy transfer. 相似文献
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Dr. Ruth Hielscher Prof. Dr. Thorsten Friedrich Prof. Dr. Petra Hellwig 《Chemphyschem》2011,12(1):217-224
The catalytic activity of the respiratory NADH:ubiquinone oxidoreductase (complex I) is based on conformational reorganizations. Herein we probe the effect of substrates on the conformational flexibility of complex I by means of 1H/2H exchange kinetics at the level of the amide proton in the mid‐infrared spectral range (1700–1500 cm?1). Slow, medium, and fast exchanging domains are distinguished that reveal different accessibilities to the solvent. Whereas amide hydrogens undergo rapid exchange with the solvent in an open structure, hydrogens experience much slower exchange when they are involved in H‐bonded structures or when they are sterically inaccessible for the solvent. The results indicate a structure that is more open in the presence of both NADH and quinon. Complementary information on the overall internal hydrogen bonding of the protein was probed in the far infrared (300–30 cm?1), a spectral range that includes a continuum mode of the hydrogen bonding signature. 相似文献
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Alice Merca Jürgen Schnack Joris van Slageren Thorsten Glaser Hartmut Bögge Veronika Hoeke Mechtild Läge Achim Müller Bernt Krebs 《Journal of Cluster Science》2013,24(4):979-988
The gadolinium (Gd) member of a new type of heteropolytungstates that contain one lanthanide and two transition metal ions in a triangular arrangement is reported. The compound NaK6Gd0.33 [((VO)2Gd(H2O)4K2(H2O)2(Na)(H2O)2)(α-B-AsW9O33)2]·24H2O (1) was prepared from acidified aqueous solutions of Na2WO4·2H2O, As2O3 and VOSO4·5H2O to which Gd3+ ions were added. The single crystal X-ray structure analysis (monoclinic, space group P21/m) shows that the anion consists of two [α-B-AsIIIW9O33]9? trilacunary Keggin-type units linked by two VO2+, one Gd3+ as well as weakly by two K+ and one Na+ ions, resulting in a sandwich-type structure with idealized C 2v symmetry. The problem of positioning crystal lattice and special polyoxometalate sites with different cations is discussed also in connection with supramolecular chemistry aspects and as an option for further research. A fit of the magnetic susceptibility yielded exchange coupling constants of J VV = ?2.55 cm?1 (anti-ferromagnetic) between the vanadium ions and J GdV = 0.6 cm?1 (ferromagnetic) between the Gd and each of the two vanadium ions. The complete magnetochemical analysis also revealed a partial occupancy of the Na+ sites in the counter-cation–water system by Gd3+ ions (0.33 Gd3+ ions in total). 相似文献