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61.
Oxidative Addition of Haloheteroarenes to Palladium(0): Concerted versus SNAr‐Type Mechanism 下载免费PDF全文
Prof. Bert U. W. Maes Dr. Stefan Verbeeck Dr. Tom Verhelst Audrey Ekomié Niklas von Wolff Dr. Guillaume Lefèvre Dr. Emily A. Mitchell Prof. Anny Jutand 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(21):7858-7865
The kinetics of the oxidative additions of haloheteroarenes HetX (X=I, Br, Cl) to [Pd0(PPh3)2] (generated from [Pd0(PPh3)4]) have been investigated in THF and DMF and the rate constants have been determined. In contrast to the generally accepted concerted mechanism, Hammett plots obtained for substituted 2‐halopyridines and solvent effects reveal a reaction mechanism dependent on the halide X of HetX: an unprecedented SNAr‐type mechanism for X=Br or Cl and a classical concerted mechanism for X=I. These results are supported by DFT studies. 相似文献
62.
Benjamin Arras Ehsan Azmoodeh Guillaume Poly Yvik Swan 《Stochastic Processes and their Applications》2019,129(7):2341-2375
We provide a bound on a distance between finitely supported elements and general elements of the unit sphere of . We use this bound to estimate the Wasserstein-2 distance between random variables represented by linear combinations of independent random variables. Our results are expressed in terms of a discrepancy measure related to Nourdin–Peccati’s Malliavin–Stein method. The main application is towards the computation of quantitative rates of convergence to elements of the second Wiener chaos. In particular, we explicit these rates for non-central asymptotic of sequences of quadratic forms and the behavior of the generalized Rosenblatt process at extreme critical exponent. 相似文献
63.
Guillaume Pisella Alec Gagnebin Prof. Dr. Jérôme Waser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(45):10199-10204
Multicomponent reactions provide efficient means to access molecular complexity. Herein, we report a copper-catalyzed three-component reaction of diazo compounds, alcohols and ethynyl benziodoxole (EBX) reagents for the synthesis of propargyl ethers. Extensive variations of the three partners of the reaction is possible, leading to highly functionalized and structurally diverse products under mild conditions. Alkynylation of a copper ylide intermediate is postulated as key step for this transformation. 相似文献
64.
Mihaela Gulea Isabelle Abrunhosa Jozef Drabowicz Guillaume Grach Matthieu Hamel Serge Masson 《Phosphorus, sulfur, and silicon and the related elements》2013,188(5-6):1267-1272
Abstract A new method to prepare enantioenriched sulfinates was developed to obtain optically active ortho-methylsulfinyl(phenylphosphonates). It consists of a diastereoselective oxidation of sulfenates to sulfinates. Additionally, preliminary results concerning the synthesis of ortho-phophonylated benzylic thiol derivatives via a new P═S to P═C [1,4]-rearrangement and a first synthetic application of these compounds are also described. 相似文献
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Michèle Postel Félix Tomi Henri Li Kam Wah Laurence Mordenti Patricia Guillaume 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4):453-457
Abstract Fe(NO)2XL and Fe(NO)X2L nitrosyl iron complexes, X = Cl, I, and L = HMPA, dppe, PPh3, activate molecular O2 to yield nitrato complexes. The phosphorous ligand is decisive for the oxidative power of these nitrates: with HMPA or dppe, oxygen transfer occurs only to phosphines. On going from HMPA to PPh3 the single nitrato complex obtained, Fe(NO)2X(OPPh3)2 selectively epoxidizes cyclohexene, and this is the first example of oxygen transfer from a nitrato ligand to an olefin. 相似文献
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Zhaoliang Cao Quanquan Mu Guillaume Dovillaire Thomas Grandin Emeric Lavergne Lifa Hu 《Liquid crystals》2013,40(10):1227-1232
The effect of twisted alignment on the phase modulation of a liquid crystal wave‐front corrector was investigated. First, the effect of twisted alignment is discussed in terms of the modulation principle of the liquid crystal molecule. Only partial incident light can be modulated because of the effect of the twisted alignment. Other unmodulated light will affect the correction accuracy and the resolution of the image. The blazed grating method is proposed to solve this problem. Adaptive correction was performed without the blazed grating method and the correction results are poor. A similar adaptive correction experiment was performed with the blazed grating method and a better correction result is obtained. The residual averaged wave‐front errors are PV = 0.101λ and RMS = 0.015λ and a resolvable image is obtained. 相似文献