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Alpha-hydroxy ketones are versatile intermediates for the synthesis of complex molecular architectures and subunits of a variety of natural products. Different approaches towards the synthesis of this important functional group combination have been elaborated. The present article summarises our research on the field of RuO4-catalysed oxidations of alkenes that resulted in the development of the first RuO4-catalysed ketohydroxylation of olefins. Mechanistic investigations of both dihydroxylation and ketohydroxylation led to the discovery of the first regioselective catalytic mono oxidation of vic-diols, which was applied in a two-step sequence of asymmetric dihydroxylation and regioselective mono oxidation to furnish enantiopure alpha-hydroxy ketones with both predictable regioselectivity and absolute configuration. 相似文献
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We prove the surjectivity of the symbol map of the Frechet algebra obtained by completing an algebra of convolution and multiplication operators in the topology generated by all L2-Sobolev norms. The proof is based on an n of Egorov's theorem valid for non-homogeneous principal symbols, discussed in [5], [6]. We use the hyperbolic equation u/t=i|D|u, 0<<1, which has its characteristic flow constant at infinity, so that no differentiability of the symbol is required there. 相似文献
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Colloid and Polymer Science - 相似文献
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Meike Koenig Tadas Kasputis Daniel Schmidt Keith B. Rodenhausen Klaus-Jochen Eichhorn Angela K. Pannier Mathias Schubert Manfred Stamm Petra Uhlmann 《Analytical and bioanalytical chemistry》2014,406(28):7233-7242
A combined setup of quartz crystal microbalance and generalized ellipsometry can be used to comprehensively investigate complex functional coatings comprising stimuli-responsive polymer brushes and 3D nanostructures in a dynamic, noninvasive in situ measurement. While the quartz crystal microbalance detects the overall change in areal mass, for instance, during a swelling or adsorption process, the generalized ellipsometry data can be evaluated in terms of a layered model to distinguish between processes occurring within the intercolumnar space or on top of the anisotropic nanocolumns. Silicon films with anisotropic nanocolumnar morphology were prepared by the glancing angle deposition technique and further functionalized by grafting of poly-(acrylic acid) or poly-(N- isopropylacrylamide) chains. Investigations of the thermoresponsive swelling of the poly-(N-isopropylacrylamide) brush on the Si nanocolumns proved the successful preparation of a stimuli-responsive coating. Furthermore, the potential of these novel coatings in the field of biotechnology was explored by investigation of the adsorption of the model protein bovine serum albumin. Adsorption, retention, and desorption triggered by a change in the pH value is observed using poly-(acrylic acid) functionalized nanostructures, although generalized ellipsometry data revealed that this process occurs only on top of the nanostructures. Poly-(N-isopropylacrylamide) is found to render the nanostructures non-fouling properties. 相似文献
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Guoxiong Hua Cameron L. Carpenter-Warren David B. Cordes Alexandra M. Z. Slawin J. Derek Woollins 《Molecules (Basel, Switzerland)》2021,26(8)
A series of N-aryl-N-(2-oxo-2-arylethyl) benzamides and cinnamides has been prepared. The reaction of the benzamides with Woollins’ reagent, a highly efficient chemoselective selenation/reduction reagent, gave the corresponding N-aryl-N-(arylenethyl) benzoselenoamides in good yields. Five representative single crystal X-ray structures are discussed. 相似文献
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Liam J. R. McGeachie Cameron L. Carpenter-Warren David B. Cordes Michael Bühl Steven J. Gray Guoxiong Hua Alexandra M. Z. Slawin J. Derek Woollins 《无机化学与普通化学杂志》2020,646(22):1795-1798
An improved route to d-block and main group NSO complexes is presented including the synthesis of the first antimony(V) complexes, (Ar3Sb(NSO)2), and copper examples [CuBipy(PPh3)NSO]. The structures of eight complexes are reported. The observed variation in M–N–S bond angles is due to the combination of orbital overlap (ligand-to-metal bonding) and the degree of ionicity of the bonding. 相似文献
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Cihang Yu Dr. Agnes Kütt Prof. Dr. Gerd-Volker Röschenthaler Dr. Tomas Lebl Dr. David B. Cordes Prof. Dr. Alexandra M. Z. Slawin Prof. Dr. Michael Bühl Prof. Dr. David O'Hagan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(45):20077-20081
We report the synthesis of all-cis 1,2,4,5-tetrakis (trifluoromethyl)- and all-cis 1,2,3,4,5,6-hexakis (trifluoromethyl)- cyclohexanes by direct hydrogenation of precursor tetrakis- or hexakis- (trifluoromethyl)benzenes. The resultant cyclohexanes have a stereochemistry such that all the CF3 groups are on the same face of the cyclohexyl ring. All-cis 1,2,3,4,5,6-hexakis(trifluoromethyl)cyclohexane is the most sterically demanding of the all-cis hexakis substituted cyclohexanes prepared to date, with a barrier (ΔG) to ring inversion calculated at 27 kcal mol−1. The X-ray structure of all-cis 1,2,3,4,5,6-hexakis(trifluoromethyl)cyclohexane displays a flattened chair conformation and the electrostatic profile of this compound reveals a large diffuse negative density on the fluorine face and a focused positive density on the hydrogen face. The electropositive hydrogen face can co-ordinate chloride (K≈103) and to a lesser extent fluoride and iodide ions. Dehydrofluorination promoted decomposition occurs with fluoride ion acting as a base. 相似文献