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21.
Marine Rémy Dr. Iwona Nierengarten Boram Park Dr. Michel Holler Dr. Uwe Hahn Dr. Jean-François Nierengarten 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(33):8492-8499
Stable pillar[5]arene-containing [2]rotaxane building blocks with pentafluorophenyl ester stoppers have been efficiently prepared on a multi-gram scale. Reaction of these building blocks with various nucleophiles gave access to a wide range of [2]rotaxanes with amide, ester or thioester stoppers in good to excellent yields. The rotaxane structure is fully preserved during these chemical transformations. Actually, the addition-elimination mechanism at work during these transformations totally prevents the unthreading of the axle moiety of the mechanically interlocked system. The stopper exchange reactions were optimized both in solution and under mechanochemical solvent-free conditions. While amide formation is more efficient in solution, the solvent-free conditions are more powerful for the transesterification reactions. Starting from a fullerene-functionalized pillar[5]arene derivative, this new strategy gave easy access to a photoactive [2]rotaxane incorporating a C60 moiety and two Bodipy stoppers. Despite the absence of covalent connectivity between the Bodipy and the fullerene moieties in this photoactive molecular device, efficient through-space excited state interactions have been evidenced in this rotaxane. 相似文献
22.
Iwona Kwiecień Grażyna Adamus Marek Kowalczuk 《Rapid communications in mass spectrometry : RCM》2012,26(23):2673-2682
23.
Iwona E. Głowacka Dorota G. Piotrowska Andrzej E. Wróblewski Aleksandra Trocha 《Tetrahedron: Asymmetry》2017,28(11):1602-1607
A simple and efficient synthetic strategy to all four enantiomerically pure diethyl 1,2-di(N-Boc-amino)propylphosphonates has been elaborated starting from the corresponding N-[(R)-(1-phenylethyl)]aziridine-(2S)- and N-[(S)-(1-phenylethyl)]aziridine-(2R)-carboxaldehydes, employing a one-pot three-components Kabachnik-Fields reaction followed by the hydrogenolytic removal of the chiral auxiliary and aziridine ring opening with simultaneous protection of the amino groups as the N-Boc derivatives. 相似文献
24.
Dr. Karolina Zelga Dr. Tomasz Pietrzak Dr. Tomasz Han Dr. Iwona Justyniak Dr. Elżbieta Chwojnowska Prof. Piotr Sobota Prof. Janusz Lewiński 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(57):14234-14239
Alkylzinc aminoalcoholates have emerged as powerful catalysts in organic synthesis and polymerization processes. Despite extensive research, difficulties in the rational design of these catalytic systems and in-depth understanding of their modes of action have hitherto been encountered. Most of the major obstacles stem largely from the relatively limited knowledge of the structure-activity relationship of zinc catalysts. In fact, the key active species are often generated in situ via the protonolysis of the alkylzinc precursors, which precludes their isolation and detailed characterization. Herein, the effectiveness of the oxygenation over the classical protonolysis in the synthesis of zinc alkylperoxides stabilized by an aminoalcoholate ligand is demonstrated. The controlled oxygenation of a tert-butylzinc complex incorporating a pridinolum (prinol) ligand leads to well-defined a dinuclear adduct of a (prinol)ZnOOtBu moiety with the parent tBuZn(prinol) complex and a novel dimer [tBuOOZn(prinol)]2 with terminal alkylperoxide groups. The observed reaction outcomes strongly depend on the reaction conditions. Although sparse examples of heteroleptic adducts of the [RZn(L)]x[ROOZn(L)]y-type are known, the herein reported homoleptic [ROOZn(L)]x aggregate is unprecedented. Strikingly, comparative studies involving reactions between tBuZn(prinol) and tert-butylhydroperoxide or ethanol revealed that the respective seemingly simple zinc alkylperoxides, or zinc alkoxides, respectively, are not accessible via the classical alcoholysis. We believe that these game-changing results concerning multifaceted chemistry of organozinc aminoalcoholates should pave the way for more rational development of various Zn-based catalytic systems. 相似文献
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26.
This paper presents a comparison of certain direct algorithms for computing the Moore-Penrose inverse, for matrices of full column rank, from the point of view of numerical stability. It is proved that the algorithm using Householder QR decomposition, implemented in floating point arithmetic, is forward stable but only conditionally mixed forward-backward stable. A similar result holds also for the Classical Gram-Schmidt algorithm with reorthogonalization (CGS2). This algorithm was developed and analyzed by Abdelmalek (BIT, 11(4):354–367, 1971) and its detailed error analysis was given in Giraud et al. (Numer. Math. 101(1):87–100, 2005). 相似文献
27.
In a route towards enantiomerically enriched 1-(β-hydroxypropyl)indoles, which are potentially useful building blocks for high value-added chemicals synthesis, a kinetic resolution approach by means of lipase-catalyzed enantioselective acylation as well as hydrolysis/methanolysis has been elaborated for the first time. The enzymatic resolution of chiral N-substituted indole-based sec-alcohols was successfully accomplished, yielding both enantiomeric forms of the employed derivatives with up to >99% enantiomeric purity via an enantioselective transesterification under mild reaction conditions. The most selective resolutions were obtained using fungal (CAL-B and TLL) and bacterial (PFL and BCL) lipases and vinyl acetate as the acyl?group donor. The synthetic protocol described herein is very simple, user-friendly and efficient, thus paving the way for future access towards more complex compounds of this type. The absolute configurations of novel enantiomeric derivatives, and thus stereoselectivity of the described enzymatic reactions were confirmed by application of CDA-based NMR methodology and single-crystal X-ray diffraction analysis. 相似文献
28.
Dr. Łukasz Mąkolski Vadim Szejko Dr. Karolina Zelga Dr. Adam Tulewicz Dr. Piotr Bernatowicz Dr. Iwona Justyniak Prof. Janusz Lewiński 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(18):5666-5674
Simple RZnOR’ alkoxides are among the first known organozinc compounds, and widespread interest in their multifaced chemistry has been driven by their fundamental significance and potential applications including various catalytic reactions. Nevertheless, their chemistry in solution and in the solid state remains both relatively poorly understood and a subject of constant debate. Herein, the synthesis and structural characterization of long-sought structural forms, a roof-like trimer [(tBuZn)3(μ-OC(H)Ph2)2(μ3-OC(H)Ph2)] and a ladder-type tetramer [(PhZn)4(μ-OC(H)Ph2)2(μ3-OC(H)Ph2)2], incorporating diphenylmethanolate as a model alkoxide ligand, are reported. Both novel aggregates are robust in the solid state and resistant towards mechanical force. By using 1H NMR and diffusion-order spectroscopy, it is demonstrated that new RZnOR’ alkoxides are kinetically labile in solution and readily undergo ligand scrambling, such as in the case of Schlenk equilibrium. The elucidated key structural issues, which have remained undiscovered for decades, significantly advance the chemistry of RZnOR’ alkoxides and should support the rational design of zinc alkoxide-based applications. 相似文献
29.
30.
Prof. Dr. Antoni W. Morawski Dr. Ewelina Kusiak-Nejman Dr. Iwona Pełech Katarzyna Ćmielewska Dr. Daniel Sibera Piotr Staciwa Dr. Agnieszka Wanag Marcin Gano Dr. Ewa Ekiert Dr. Joanna Kapica-Kozar Kordian Witkowski Prof. Dr. Urszula Narkiewicz 《ChemistryOpen》2022,11(4):e202100262
A new approach to hydrogen production from water is described. This simple method is based on carbon dioxide-mediated water decomposition under UV radiation. The water contained dissolved sodium hydroxide, and the solution was saturated with gaseous carbon dioxide. During saturation, the pH decreased from about 11.5 to 7–8. The formed bicarbonate and carbonate ions acted as scavengers for hydroxyl radicals, preventing the recombination of hydroxyl and hydrogen radicals and prioritizing hydrogen gas formation. In the presented method, not yet reported in the literature, hydrogen production is combined with carbon dioxide. For the best system with alkaline water (0.2 m NaOH) saturated with CO2 under UV-C, the hydrogen production amounted to 0.6 μmol h−1 during 24 h of radiation. 相似文献