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51.
Although known since the 1950s, free-radical carbonylation has not received much attention until only recently. In the last few years the application of modern free-radical techniques has revealed the high synthetic potential of this reaction as a tool for introducing CO into organic molecules. Clearly now is the time for a renaissance of this chemistry. Under standard conditions (tributyltin hydride/CO) primary, secondary, as well as tertiary alkyl bromides and iodides can be efficiently converted into the corresponding aldehydes. Aromatic and α,β-unsaturated aldehydes can also be prepared from the parent aromatic and vinylic iodides. If the reaction is carried out in the presence of alkenes containing an electron-withdrawing substituent, the initially formed acyl radical subsequently adds to the alkene, leading to a general method for the synthesis of unsymmetrical ketones. This three-component coupling reaction can be extended successfully to allyltin-mediated reactions. Thus, β,γ-enones can be prepared from organic halides, CO, and allyltributylstannanes. In a remarkable one-pot procedure alkyl halides can be treated with a mixture of alkene, allyltributylstannane, and carbon monoxide in a four-component coupling reaction that provides β-functionalized δ,?-unsaturated ketones by the formation of three new C? C bonds. The reaction of 4-pentenyl radicals with CO leads to acyl radical cyclization, which provides a useful method for the synthesis of cyclopentanones. Certain useful one-electron oxidations can be combined efficiently with free-radical carbonylations. These findings and others discussed in this article clearly demonstrate that free-radical carbonylation can now be considered a practical alternative to transition metal mediated carbonylation. 相似文献
52.
Masaki Shimizu Prof. Dr. Takuya Kurahashi Dr. Katsuhiro Shimono Dr. Kei Tanaka Ikuhiro Nagao Shin‐ichi Kiyomoto Tamejiro Hiyama Prof. Dr. 《化学:亚洲杂志》2007,2(11):1400-1408
Treatment of 1,1‐bis(pinacolatoboryl)ethene with an excess of 1‐bromo‐1‐lithioethene gave 2,3‐bis(pinacolatoboryl)‐1,3‐butadiene in high yield. Palladium‐catalyzed cross‐coupling of the resulting diborylbutadiene with aryl iodides took place smoothly in the presence of a catalytic amount of Pd(OAc)2/PPh3 and aqueous KOH to give 2,3‐diaryl‐1,3‐butadienes in good yields. The coupling reaction with commercially available 4‐acetoxyphenylmethyl chloride under the same conditions followed by hydrolysis of the acetyl groups gave anolignan B in a one‐pot manner. A variety of [3]‐ to [6]dendralenes were synthesized by palladium‐catalyzed coupling of the diene or 1,1‐bis(pinacolato)borylethene with alkenyl or dienyl halides, respectively, in good yields. 相似文献
53.
A History of Fischer-Tropsch Wax Upgrading at BP—— from Catalyst Screening Studies to Full Scale Demonstration in Alaska 下载免费PDF全文
John P. Collins Joep J. H. M. Font Freidet Barry Nay 《天然气化学杂志》2006,15(1):1-10
Conversion of Fischer-Tropsch wax into high quality synthetic crude or finished transportation fuels such as premium diesel has been studied over the past 15 years within BP. Catalyst screening and selection was carried out in dedicated micro-reactors and pilot plants, whose designs are critical to the performance selection. Variation in catalyst composition and defining the gas to oil feed ratios with the operating temperature are a few of the parameters studied. Product selection and maximizing diesel yield combined with stability (catalyst life) were the ultimate drivers. The selected catalyst was then tested under commercial conditions in a dedicated 300 barrel per day demonstration plant. The products were also tested in engines to assess their combustion characteristics. 相似文献
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Effect of Headgroups on Small‐Ion Permeability across Archaea‐Inspired Tetraether Lipid Membranes 下载免费PDF全文
Takaoki Koyanagi Dr. Geoffray Leriche Alvin Yep David Onofrei Prof. Gregory P. Holland Prof. Michael Mayer Prof. Jerry Yang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(24):8074-8077
This paper examines the effects of four different polar headgroups on small‐ion membrane permeability from liposomes comprised of Archaea‐inspired glycerolmonoalkyl glycerol tetraether (GMGT) lipids. We found that the membrane‐leakage rate across GMGT lipid membranes varied by a factor of ≤1.6 as a function of headgroup structure. However, the leakage rates of small ions across membranes comprised of commercial bilayer‐forming 1‐palmitoyl‐2‐oleoyl‐sn‐glycerol (PO) lipids varied by as much as 32‐fold within the same series of headgroups. These results demonstrate that membrane leakage from GMGT lipids is less influenced by headgroup structure, making it possible to tailor the structure of the polar headgroups on GMGT lipids while retaining predictable leakage properties of membranes comprised of these tethered lipids. 相似文献
57.
Enhancing the Value of Free Metals in the Synthesis of Lanthanoid Formamidinates: Is a Co‐oxidant Needed? 下载免费PDF全文
Prof. Dr. Glen B. Deacon Prof. Dr. Peter C. Junk Dr. Daniel Werner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(1):160-173
Treatment of N,N′‐bis(aryl)formamidines (ArFormH), N,N′‐bis(2,6‐difluorophenyl)formamidine (DFFormH) or N,N′‐bis(2,6‐diisopropylphenyl)formamidine (DippFormH), with europium metal in CH3CN is an efficient synthesis of the divalent complexes: [{Eu(DFForm)2(CH3CN)2}2] ( Eu1 ) or [Eu(DippForm)2(CH3CN)4] ( Eu2 ). The synthetic method was extended to ytterbium, but the metal required activation by addition of Hg0. With DFFormH in CH3CN, [{Yb(DFForm)2(CH3CN)}2] ( Yb1 ) was obtained in good yield, and [Yb(DFForm)2(thf)3] ( Yb3 ) was obtained from a synthesis in CH3CN/THF. Thus, this synthetic method completely circumvents the use of either salt metathesis, or redox transmetallation/protolysis (RTP) protocols to prepare divalent rare‐earth formamidinates. Heating Yb1 in PhMe/C6D6 resulted in decomposition to trivalent products, including one from a CH3CN activation process. For a synthetic comparison, divalent ytterbium DFForm and DippForm complexes were synthesised by RTP reactions between Yb0, Hg(R)2 (R=Ph, C6F5), and ArFormH in THF, leading to the isolation of either [Yb(DFForm)2(thf)3] ( Yb3 ), or the first five coordinate rare‐earth formamidinate complex [Yb(DippForm)2(thf)] ( Yb4 b ), and, from adjustment of the stoichiometry, trivalent [Yb(DFForm)3(thf)] ( Yb6 ). Oxidation of Yb3 with benzophenone (bp), or halogenating agents (TiCl4(thf)2, Ph3CCl, C2Cl6) gave [Yb(DFForm)3(bp)] or [Yb(DFForm)2Cl(thf)2], respectively. Furthermore, the structural chemistry of divalent ArForm complexes has been substantially broadened. Not only have the highest and lowest coordination numbers for divalent rare‐earth ArForm complexes been achieved in Eu2 and Yb4 b , respectively, but also dimeric Eu1 and Yb1 have highly unusual ArForm bridging coordination modes, either perpendicular μ‐1κ(N:N′):2κ(N:N′) in Eu1 , or the twisted μ‐1κ(N:N′):2κ(N′:F′) DFForm coordination in Yb1 , both unprecedented in divalent rare‐earth ArForm chemistry and in the wider divalent rare‐earth amidinate field. 相似文献
58.
The accuracy of boundary conditions for computational aeroacoustics is a well‐known challenge, due in part to the necessity of truncating the flow domain and replacing the analytical boundary conditions at infinity with numerical boundary conditions. In particular, the inflow boundary condition involving turbulent velocity or scalar fields is likely to introduce spurious waves into the domain, therefore degrading the flow behavior and deteriorating the physical acoustic waves. In this work, a method to generate low‐noise, divergence‐free, synthetic turbulence for inflow boundary conditions is proposed. It relies on the classical view of turbulence as a superposition of random eddies convected with the mean flow. Within the proposed model, the vector potential and the requirement that the individual eddies must satisfy the linearized momentum equations about the mean flow are used. The model is tested using isolated eddies convected through the inflow boundary and an experimental benchmark data for spatially decaying isotropic turbulence. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
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