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131.
Van De Walle CG 《Physical review letters》2000,85(5):1012-1015
Zinc oxide, a wide-band-gap semiconductor with many technological applications, typically exhibits n-type conductivity. The cause of this conductivity has been widely debated. A first-principles investigation, based on density functional theory, produces strong evidence that hydrogen acts as a source of conductivity: it can incorporate in high concentrations and behaves as a shallow donor. This behavior is unexpected and very different from hydrogen's role in other semiconductors, in which it acts only as a compensating center and always counteracts the prevailing conductivity. These insights have important consequences for control and utilization of hydrogen in oxides in general. 相似文献
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Unnatural Amino Acid Synthesis Enabled by the Regioselective Cobalt(III)‐Catalyzed Intermolecular Carboamination of Alkenes
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Andreas Lerchen Tobias Knecht Dr. Constantin G. Daniliuc Prof. Dr. Frank Glorius 《Angewandte Chemie (International ed. in English)》2016,55(48):15166-15170
Herein, we report an unprecedented regioselective and entirely atom‐economic cobalt(III)‐catalyzed method for the non‐annulative, intermolecular carboamination of alkenes. The methodology enables the direct synthesis of unnatural amino acid derivatives and proceeds under redox‐neutral conditions with a completely regioselective C?C bond and C?N bond formation. Furthermore, this reaction exemplifies the inherently different mechanistic behavior of the Cp*CoIII catalyst and its Cp*RhIII counterpart, especially towards β‐H‐elimination. 相似文献
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Lewis Acid Catalyzed Stereoselective Dearomative Coupling of Indolylboron Ate Complexes with Donor–Acceptor Cyclopropanes and Alkyl Halides
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Saikat Das Dr. Constantin G. Daniliuc Prof. Dr. Armido Studer 《Angewandte Chemie (International ed. in English)》2018,57(15):4053-4057
Indolylboron ate complexes readily generated from 2‐lithioindoles and boronic esters underwent multicomponent dearomative coupling with D‐A cyclopropanes and alkyl halides in the presence of Sc(OTf)3 as a catalyst. The reactions proceeded with complete diastereoselectivity and excellent stereospecificity to provide indolines containing three contiguous stereocenters. The valuable boronic ester moiety remains in the product and allows for subsequent functionalization. 相似文献
138.
Efficient Synthesis of Arylated Furans by a Sequential Rh‐Catalyzed Arylation and Cycloisomerization of Cyclopropenes
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Dr. Xiaoming Wang Andreas Lerchen Dr. Constantin G. Daniliuc Prof. Frank Glorius 《Angewandte Chemie (International ed. in English)》2018,57(6):1712-1716
A novel and efficient strategy for the synthesis of arylated furans was successfully developed by a RhIII‐catalyzed coupling of N‐phenoxyacetamides and cyclopropenyl esters. Mechanistic investigation reveals that the arylated furans are formed via arylation of the cyclopropenyl esters followed by cycloisomerization. 相似文献
139.
Contra‐Thermodynamic,Photocatalytic E→Z Isomerization of Styrenyl Boron Species: Vectors to Facilitate Exploration of Two‐Dimensional Chemical Space
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M. Chem. John J. Molloy Dr. Jan B. Metternich Dr. Constantin G. Daniliuc Dr. Allan J. B. Watson Prof. Dr. Ryan Gilmour 《Angewandte Chemie (International ed. in English)》2018,57(12):3168-3172
Designing strategies to access stereodefined olefinic organoboron species is an important synthetic challenge. Despite significant advances, there is a striking paucity of routes to Z‐α‐substituted styrenyl organoborons. Herein, this strategic imbalance is redressed by exploiting the polarity of the C(sp2)?B bond to activate the neighboring π system, thus enabling a mild, traceless photocatalytic isomerization of readily accessible E‐α‐substituted styrenyl BPins to generate the corresponding Z‐isomers with high fidelity. Preliminary validation of this contra‐thermodynamic E→Z isomerization is demonstrated in a series of stereoretentive transformations to generate Z‐configured trisubstituted alkenes, as well as in a concise synthesis of the anti‐tumor agent Combretastatin A4. 相似文献
140.
Ruben Van Lommel Jonathan Bock Constantin G. Daniliuc Ulrich Hennecke Frank De Proft 《Chemical science》2021,12(22):7746
The halolactonization reaction is one of the most common electrophilic addition reactions to alkenes. The mechanism is generally viewed as a two-step pathway, which involves the formation of an ionic intermediate, in most cases a haliranium ion. Recently, an alternative concerted mechanism was proposed, in which the nucleophile of the reaction played a key role in the rate determining step by forming a pre-polarized complex with the alkene. This pathway was coined the nucleophile-assisted alkene activation (NAAA) mechanism. Metadynamics simulations on a series of model halolactonization reactions were used to obtain the full dynamic trajectory from reactant to product and investigate the explicit role of the halogen source and solvent molecules in the mechanism. The results in this work ratify the occasional preference of a concerted mechanism over the classic two-step transformation under specific reaction conditions. Nevertheless, as the stability of both the generated substrate cation and counter-anion increase, a transition towards the classic two-step mechanism was observed. NCI analyses on the transition states revealed that the activating role of the nucleophile is independent of the formation and stability of the intermediate. Additionally, the dynamic insights obtained from the metadynamics simulations and NCI analyses employed in this work, unveiled the presence of syn-directing noncovalent interactions, such as hydrogen bonding, between the alkenoic acid and the halogen source, which rationalized the experimentally observed diastereoselectivities. Explicit noncovalent interactions between the reactants and a protic solvent or basic additive are able to disrupt these syn-directing noncovalent interactions, affecting the diastereoselective outcome of the reaction. Ab initio dynamics of the halolactonization reaction provide insights into the diastereoselectivity of the reaction. Noncovalent interactions between the substrate, halogen source and solvent are revealed to direct the formation of the syn-product. 相似文献