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Total Synthesis,Stereochemical Assignment,and Field‐Testing of the Sex Pheromone of the Strepsipteran Xenos peckii 下载免费PDF全文
Dr. Huimin Zhai Michael Hrabar Regine Gries Prof. Gerhard Gries Prof. Robert Britton 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(18):6190-6193
The sex pheromone of the endoparasitoid insect Xenos peckii (Strepsiptera: Xenidae) was recently identified as (7E,11E)‐3,5,9,11‐tetramethyl‐7,11‐tridecadienal. Herein we report the asymmetric synthesis of three candidate stereostructures for this pheromone using a synthetic strategy that relies on an sp3–sp2 Suzuki–Miyaura coupling to construct the correctly configured C7‐alkene function. Comparison of 1H NMR spectra derived from the candidate stereostructures to that of the natural sex pheromone indicated a relative configuration of (3R*,5S*,9R*). Chiral gas chromatographic (GC) analyses of these compounds supported an assignment of (3R,5S,9R) for the natural product. Furthermore, in a 16‐replicate field experiment, traps baited with the synthetic (3R,5S,9R)‐enantiomer alone or in combination with the (3S,5R,9S)‐enantiomer captured 23 and 18 X. peckii males, respectively (mean±SE: 1.4±0.33 and 1.1±0.39), whereas traps baited with the synthetic (3S,5R,9S)‐enantiomer or a solvent control yielded no captures of males. These strong field trapping data, in combination with spectroscopic and chiral GC data, unambiguously demonstrate that (3R,5S,9R,7E,11E)‐3,5,9,11‐tetramethyl‐7,11‐tridecadienal is the X. peckii sex pheromone. 相似文献
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Back Cover: Activation of Elemental Sulfur at a Two‐Coordinate Platinum(0) Center (Chem. Eur. J. 36/2016) 下载免费PDF全文
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Seonghwa Jeong Eunji Park Jiyeon Kim Seok Bae Park Dr. Sung Hoon Kim Prof. Wonyoung Choe Prof. Joonghan Kim Prof. Young S. Park 《Angewandte Chemie (International ed. in English)》2023,62(50):e202314148
Increasing the chemical diversity of organic semiconductors is essential to develop efficient electronic devices. In particular, the replacement of carbon-carbon (C−C) bonds with isoelectronic boron-nitrogen (B−N) bonds allows precise modulation of the electronic properties of semiconductors without significant structural changes. Although some researchers have reported the preparation of B2N2 anthracene derivatives with two B−N bonds, no compounds with continuous multiple BN units have been prepared yet. Herein, we report the synthesis and characterization of a B2N2 anthracene derivative with a BNBN unit formed by converting the BOBN unit at the zigzag edge. Compared to the all-carbon analogue 2-phenylanthracene, BNBN anthracene exhibits significant variations in the C−C bond length and a larger highest occupied molecular orbital–lowest unoccupied molecular orbital energy gap. The experimentally determined bond lengths and electronic properties of BNBN anthracene are confirmed through theoretical calculations. The BOBN anthracene organic light-emitting diode, used as a blue host, exhibits a low driving voltage. The findings of this study may facilitate the development of larger acenes with multiple BN units and potential applications in organic electronics. 相似文献
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Johannes Kretsch Anne-Kathrin Kreyenschmidt Timo Schillmöller Dr. Märt Lõkov Dr. Regine Herbst-Irmer Prof. Dr. Ivo Leito Prof. Dr. Dietmar Stalke 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(38):9858-9865
A novel sterically demanding bis(4-benzhydryl-benzoxazol-2-yl)methane ligand 6 (4−BzhH2BoxCH2) was gained in a straightforward six-step synthesis. Starting from this ligand monomeric [M(4-BzhH2BoxCH)] (M=Na ( 7 ), K ( 81 )) and dimeric [{M(4-BzhH2BoxCH)}2] (M=K ( 82 ), Rb ( 9 ), Cs ( 10 )) alkali metal complexes were synthesised by deprotonation. Abstraction of the potassium ion of 8 by reaction with 18-crown-6 resulted in the solvent separated ion pair [{(THF)2K@(18-crown-6)}{bis(4-benzhydryl-benzoxazol-2-yl)methanide}] ( 11 ), including the energetically favoured monoanionic (E,E)-(4-BzhH2BoxCH) ligand. Further reaction of 4−BzhH2BoxCH2 with three equivalents KH and two equivalents 18-crown-6 yielded polymeric [{(THF)2K@(18-crown-6)}{K@(18-crown-6)K(4-BzhBoxCH)}]n (n→∞) ( 12 ) containing a trianionic ligand. The neutral ligand and herein reported alkali complexes were characterised by single X-ray analyses identifying the latter as a promising precursor for low-valent main group complexes. 相似文献
6.
Marina Huber-Gedert Dr. Michał Nowakowski Dr. Ahmet Kertmen Dr. Lukas Burkhardt Dr. Natalia Lindner Dr. Roland Schoch Dr. Regine Herbst-Irmer Dr. Adam Neuba Lennart Schmitz Tae-Kyu Choi Dr. Jacek Kubicki Prof. Dr. Wojciech Gawelda Prof. Dr. Matthias Bauer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(38):9905-9918
A new base metal iron-cobalt dyad has been obtained by connection between a heteroleptic tetra-NHC iron(II) photosensitizer combining a 2,6-bis[3-(2,6-diisopropylphenyl)imidazol-2-ylidene]pyridine with 2,6-bis(3-methyl-imidazol-2-ylidene)-4,4′-bipyridine ligand, and a cobaloxime catalyst. This novel iron(II)-cobalt(III) assembly has been extensively characterized by ground- and excited-state methods like X-ray crystallography, X-ray absorption spectroscopy, (spectro-)electrochemistry, and steady-state and time-resolved optical absorption spectroscopy, with a particular focus on the stability of the molecular assembly in solution and determination of the excited-state landscape. NMR and UV/Vis spectroscopy reveal dissociation of the dyad in acetonitrile at concentrations below 1 mM and high photostability. Transient absorption spectroscopy after excitation into the metal-to-ligand charge transfer absorption band suggests a relaxation cascade originating from hot singlet and triplet MLCT states, leading to the population of the 3MLCT state that exhibits the longest lifetime. Finally, decay into the ground state involves a 3MC state. Attachment of cobaloxime to the iron photosensitizer increases the 3MLCT lifetime at the iron centre. Together with the directing effect of the linker, this potentially makes the dyad more active in photocatalytic proton reduction experiments than the analogous two-component system, consisting of the iron photosensitizer and Co(dmgH)2(py)Cl. This work thus sheds new light on the functionality of base metal dyads, which are important for more efficient and sustainable future proton reduction systems. 相似文献
7.
In two-dimensional electrides, anionic electrons are spatially confined in interlayer regions with high density, comparable to metals, and they are highly mobile, just as free electrons, resembling hyperbolic metamaterials with metal-dielectric multilayered structures. In this work, two-dimensional electride materials MgONa and CaONa are proposed as good natural hyperbolic materials. By using the first-principles calculations based on density functional theory (DFT), the electronic structures, stabilities, and optical properties of two-dimensional electride materials XONa (X=Mg, Ca) are investigated. Our results show that they are stable in 1-monolayer (1-ML) structures as well as in bulk states. They exhibit hyperbolic dispersions from visible to near infrared spectral range with high qualities up to about 700, which is two orders-of-magnitude larger than the preceding bulk hyperbolic materials. Numerical results reveal that they exhibit negative refraction with low losses. Their high-quality hyperbolic responses over a wide spectral range pave the way of broad photonic applications as natural hyperbolic materials. 相似文献
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Dr. Mohd Nazish Dr. Mujahuddin M. Siddiqui Dr. Samir Kumar Sarkar Dr. Annika Münch Christina M. Legendre Dr. Regine Herbst-Irmer Prof. Dietmar Stalke Prof. Dr. Herbert W. Roesky 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(5):1744-1752
This work describes the synthesis and coordination behavior of a new mixed-donor ligand PhC(NtBu)2SiC6H4PPh2 ( 1 ) containing both silylene and phosphine donor sites. Ligand 1 was synthesized from a reaction of ortho-lithiated diphenylphosphinobenzene (LiC6H4PPh2) with chlorosilylene (PhC(NtBu)2SiCl). Treatment of 1 with Se and GeCl2 resulted in SiIV compounds 2 and 3 by selective oxidation of the silylene donor. This strong σ-donor ligand induces dissociation of CuCl and PhBCl2 leading to formation of ionic complexes 4 and 5 respectively. The reaction of 1 with ZnCl2 and AlCl3 resulted in the formation of chelate complexes 5 and 7 , respectively, while treatment with EtAlCl2 and GaCl3 forms monodentate complexes 8 and 9 . X-ray analysis of 4 showed that the copper is in the spiro center of the two five-membered rings. Moreover, the copper(I)chloride has not been oxidized but dissociates to Cu+ and [CuCl2]−. All the compounds are well characterized by mass spectrometry, elemental analysis, NMR spectroscopy, and single-crystal X-ray diffraction studies. 相似文献