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81.
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Two libraries of enantiomerically pure imidazolium salts bearing an oxazoline unit were synthesized. Deprotonation of the imidazolium salts and complexation of the resulting oxazoline-carbene ligands to iridium(I) was achieved in one step by mixing the imidazolium salts with NaOtBu and [(eta(4)-cod)IrCl](2) in THF at room temperature. The air-stable complexes were purified by flash chromatography. All complexes were analyzed by two-dimensional (2D) NMR methods and one compound from each family was characterized by X-ray structure analysis. The two libraries of iridium complexes were successfully tested in the asymmetric hydrogenation of unfunctionalized and functionalized olefins. Enantioselectivities of up to 90 % ee were obtained with trans-alpha-methylstilbene. Upon complexation of imidazolium salt 15 p with R(1) = phenyl, C-H bond activation of the phenyl ring gave rise to iridium(III) complex 17, which was fully characterized by NMR spectroscopy and X-ray structure analysis. Complex 17 proved to be catalytically inactive in the hydrogenation. 相似文献
83.
Wang J Li H Lou B Zu L Guo H Wang W 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(16):4321-4332
Chiral (S)-pyrrolidine trifluoromethanesulfonamide has been shown to serve as an effective catalyst for direct Michael addition reactions of aldehydes and ketones with nitroolefins. A wide range of aldehydes and ketones as Michael donors and nitroolefins as acceptors participate in the process, which proceeds with high levels of enantioselectivity (up to 99 % ee) and diastereoselectivity (up to 50:1 d.r.). The methodology has been employed successfully in an efficient synthesis of the potent H(3) agonist Sch 50917. In addition, a practical three-step procedure for the preparation of (S)-pyrrolidine trifluoromethanesulfonamide has been developed. The high levels of stereochemical control attending Michael addition reactions catalyzed by this pyrrolidine sulfonamide, have been investigated by using ab initio and density functional methods. Transition state structures for the rate-limiting C--C bond-forming step, corresponding to re- and si-face addition to the reactive conformation of the key enamine intermediates have been calculated. Analysis of these structures indicates that hydrogen bonding plays an important role in catalysis and that the energy barrier for si-face attack in reactions of aldehydes to form 2R,3S products is lower than that for the re-face attack leading to 2S,3R products. In contrast, the energy barrier for re-face addition is lower than that for si-face addition in reactions of ketones. The computational results, which are in good agreement with the experimental observations, are discussed in the context of the stereochemical course of these Michael addition reactions. 相似文献
84.
多通道磁共振成像方法采用多个接收线圈同时欠采样k空间以加快成像速度,并基于后处理算法重建图像,但在较高加速因子时,其图像重建质量仍然较差.本文提出了一种基于PCAU-Net的快速多通道磁共振成像方法,将单通道实数U型卷积神经网络拓展到多通道复数卷积神经网络,设计了一种结构不对称的U型网络结构,通过在解码部分减小网络规模以降低模型的复杂度.PCAU-Net网络在跳跃连接前增加了1×1卷积,以实现跨通道信息交互.输入和输出之间利用残差连接为误差的反向传播提供捷径.实验结果表明,使用规则和随机采样模板,在不同加速因子时,相比常规的GRAPPA重建算法和SPIRiT重建方法,本文提出的PCAU-Net方法可高质量重建出磁共振复数图像,并且相比于PCU-Net方法,PCAU-Net减少了模型参数、缩短了训练时间. 相似文献
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Wen Shao He Li Chuan Liu Prof. Dr. Chen‐Jiang Liu Prof. Dr. Shu‐Li You 《Angewandte Chemie (International ed. in English)》2015,54(26):7684-7687
The first copper‐catalyzed intermolecular dearomatization of indoles by an asymmetric propargylic substitution reaction was developed. This method provides a highly efficient synthesis of versatile furoindoline and pyrroloindoline derivatives containing a quaternary carbon stereogenic center and a terminal alkyne moiety with up to 86 % yield and 98 % ee. 相似文献
89.
Development of Ar‐BINMOL‐Derived Atropisomeric Ligands with Matched Axial and sp3 Central Chirality for Catalytic Asymmetric Transformations 下载免费PDF全文
Recently, academic chemists have renewed their interest in the development of 1,1′‐binaphthalene‐2,2′‐diol (BINOL)‐derived chiral ligands. Six years ago, a working hypothesis, that the chirality matching of hybrid chirality on a ligand could probably lead to high levels of stereoselective induction, prompted us to use the axial chirality of BINOL derivatives to generate new stereogenic centers within the same molecule with high stereoselectivity, obtaining as a result sterically favorable ligands for applications in asymmetric catalysis. This Personal Account describes our laboratory's efforts toward the development of a novel class of BINOL‐derived atropisomers bearing both axial and sp3 central chirality, the so‐called Ar‐BINMOLs, for asymmetric synthesis. Furthermore, on the basis of the successful application of Ar‐BINMOLs and their derivatives in asymmetric catalysis, the search for highly efficient and enantioselective processes also compelled us to give special attention to the BINOL‐derived multifunctional ligands with multiple stereogenic centers for use in catalytic asymmetric reactions.
90.
Prof. Michael North Marta Omedes‐Pujol Courtney Williamson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(37):11367-11375
The asymmetric addition of trimethylsilyl cyanide to aldehydes can be catalysed by Lewis acids and/or Lewis bases, which activate the aldehyde and trimethylsilyl cyanide, respectively. It is not always apparent from the structure of the catalyst whether Lewis acid or Lewis base catalysis predominates. To investigate this in the context of using salen complexes of titanium, vanadium and aluminium as catalysts, a Hammett analysis of asymmetric cyanohydrin synthesis was undertaken. When Lewis acid catalysis is dominant, a significantly positive reaction constant is observed, whereas reactions dominated by Lewis base catalysis give much smaller reaction constants. [{Ti(salen)O}2] was found to show the highest degree of Lewis acid catalysis, whereas two [VO(salen)X] (X=EtOSO3 or NCS) complexes both displayed lower degrees of Lewis acid catalysis. In the case of reactions catalysed by [{Al(salen)}2O] and triphenylphosphine oxide, a non‐linear Hammett plot was observed, which is indicative of a change in mechanism with increasing Lewis base catalysis as the carbonyl compound becomes more electron‐deficient. These results suggested that the aluminium complex/triphenylphosphine oxide catalyst system should also catalyse the asymmetric addition of trimethylsilyl cyanide to ketones and this was found to be the case. 相似文献