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1.
Alexandre Genoux Dr. Jorge A. González Dr. Estíbaliz Merino Prof. Dr. Cristina Nevado 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18037-18042
A new family of phosphine-ligated dicyanoarylgold(III) complexes has been prepared and their reactivity towards reductive elimination has been studied in detail. Both, a highly positive entropy of activation and a primary 12/13C KIE suggest a late concerted transition state while Hammett analysis and DFT calculations indicate that the process is asynchronous. As a result, a distinct mechanism involving an asynchronous concerted reductive elimination for the overall C(sp2)−C(sp)N bond forming reaction is characterized herein, for the first time, complementing previous studies reported for C(sp3)−C(sp3), C(sp2)−C(sp2), and C(sp3)−C(sp2) bond formation processes taking place on gold(III) species. 相似文献
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Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes 下载免费PDF全文
María González‐Esguevillas Ana Pascual‐Escudero Dr. Javier Adrio Prof. Dr. Juan C. Carretero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4561-4565
The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine. 相似文献
4.
AlIII‐Catalysed Formation of Poly(limonene)carbonate: DFT Analysis of the Origin of Stereoregularity 下载免费PDF全文
Leticia Peña Carrodeguas Joan González‐Fabra Dr. Fernando Castro‐Gómez Prof. Dr. Carles Bo Prof. Dr. Arjan W. Kleij 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(16):6115-6122
Amino‐triphenolate derived AlIII complexes combined with suitable nucleophiles have been investigated as binary catalysts for the coupling of limonene oxide and carbon dioxide to afford alternating polycarbonates. These catalysts are able to produce stereoregular, perfectly alternating trans‐polymers from cis‐limonene oxide, whereas the pure trans isomer and cis/trans mixture give rise to lower degrees of stereoregularity. The best AlIII catalyst shows the potential to mediate the conversion of both stereoisomers of limonene oxide with high conversion levels of up to 71 % under neat conditions, indicating the high degree of robustness and atom‐efficiency of this catalytic process. Computational studies have revealed unique features of the binary catalyst system, among which is the preferred nucleophilic attack on the quaternary carbon centre in the limonene oxide substrate. 相似文献
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Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis 下载免费PDF全文
Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
8.
Juan Carlos López-López Dr. Delia Bautista Dr. Pablo González-Herrero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(49):11307-11315
A stereoselective synthetic route to homo- and heteroleptic facial tris-cyclometalated PtIV complexes is reported, involving the oxidative addition of 2-(2-pyridyl)- or 2-(1-isoquinolinyl)benzenediazonium salts to cis-[Pt(C^N)2] precursors, with C^N=cyclometalated 2-(p-tolyl)pyridine (tpy), 2-phenylquinoline (pq), 2-(2-thienyl)pyridine or 1-phenylisoquinoline (piq), to produce labile diazenide intermediates that undergo photochemical or thermal elimination of N2. The method allows the preparation of derivatives bearing cyclometalated ligands of low π–π* transition energies. The new complexes exhibit phosphorescence in fluid solution at room temperature arising from triplet ligand-centered (3LC) excited states, which, in the cases of the heteroleptic derivatives, involve the ligand with the lowest π–π* gap. The heteroleptic piq derivatives exhibit fluorescence and dual phosphorescence from different ligand-centered excited states in rigid media, demonstrating the potential of cyclometalated PtIV complexes as multi-emissive materials. 相似文献
9.
Dr. José A. González-Delgado Dr. Miguel A. Romero Dr. Francisco Boscá Dr. Jesús F. Arteaga Prof. Dr. Uwe Pischel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(62):14229-14235
The light-gated organocatalysis via the release of 4-N,N-dimethylaminopyridine (DMAP) by irradiation of the [Ru(bpy)2(DMAP)2]2+ complex with visible light was investigated. As model reaction the acetylation of benzyl alcohols with acetic anhydride was chosen. The pre-catalyst releases one DMAP molecule on irradiation at wavelengths longer than 455 nm. The photochemical process was characterized by steady-state irradiation and ultrafast transient absorption spectroscopy. The latter enabled the observation of the 3MLCT state and the spectral features of the penta-coordinated intermediate [Ru(bpy)2(DMAP)]2+. The released DMAP catalyzes the acetylation of a wide range of benzyl alcohols with chemical yields of up to 99 %. Control experiments revealed unequivocally that it is the released DMAP which takes the role of the catalyst. 相似文献
10.
Hélène Beucher Dr. Sudhir Kumar Dr. Roopender Kumar Dr. Estíbaliz Merino Wei-Hsu Hu Gerrit Stemmler Sergio Cuesta-Galisteo Dr. Jorge A. González Léonard Bezinge Dr. Jakub Jagielski Dr. Chih-Jen Shih Prof. Dr. Cristina Nevado 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(72):17604-17612
Efficient OLED devices have been fabricated using organometallic complexes of platinum group metals. Still, the high material cost and low stability represent central challenges for their application in commercial display technologies. Based on its innate stability, gold(III) complexes are emerging as promising candidates for high-performance OLEDs. Here, a series of alkynyl-, N-heterocyclic carbene (NHC)- and aryl-gold(III) complexes stabilized by a κ3-(N^C^C) template have been prepared and their photophysical properties have been characterized in detail. These compounds exhibit good photoluminescence quantum efficiency (ηPL) of up to 33 %. The PL emission can be tuned from sky-blue to yellowish green colors by variations on both the ancillary ligands as well as on the pincer template. Further, solution-processable OLED devices based on some of these complexes display remarkable emissive properties (ηCE 46.6 cd.A−1 and ηext 14.0 %), thus showcasing the potential of these motifs for the low-cost fabrication of display and illumination technologies. 相似文献