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Efficient control of regioselectivity is a key concern in transition-metal-catalyzed direct C–H functionalization reactions. Various strategies for regiocontrol have been established by tuning the selectivity of the C–H activation step as a common mode. Herein, we present our study on an alternative mode of regiocontrol, in which the selectivity of the C–H activation step is no longer a key concern. We found that, in a reaction where the C–H activation step exhibits a different regio-preference from the subsequent functionalization step, a ligand-enabled switch of the regioselectivity-determining step could provide efficient regiocontrol. This mode has been exemplified by the Pd(ii)-catalyzed aerobic oxidative Heck reaction of indoles, in which a ligand-controlled C3-/C2-selectivity was achieved for the first time by the development of sulfoxide-2-hydroxypyridine (SOHP) ligands.Ligand-enabled switch of the regioselectivity-determining step allowed for efficient regiocontrol in the aerobic oxidative Heck reaction of indole. 相似文献
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This study is concerned with a new,explicit approach by means of which forms of the large strain elastic potential for multiaxial rubberlike elasticity may be obtained based on data for a single deformation mode.As a departure from usual studies,here for the first time errors may be estimated and rendered minimal for all possible deformation modes and,furthermore,failure behavior may be incorporated.Numerical examples presented are in accurate agreement with Treloar's well-known data. 相似文献
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Peng-Yan Gui Xiao-Hui Yan Wen-Juan Yuan Yuan-Liang Ma Xiao Ding Shuai Liu 《Natural product research》2019,33(19):2830-2836
A new A, D-seco limonoid, named 12-acetyloxyperforatin (1), along with three known ones, were isolated from the leaves of Harrisonia perforata. Their structures were elucidated on the basis of spectroscopic analysis, including extensive NMR techniques and computational modelling. These compounds showed no inhibitory activity against the 11β-HSD1 enzyme. 相似文献
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目的:探讨等候区手术患者家属的心理影响因素及其干预措施.方法:通过临床护理实践及查阅相关文献进行总结分析.结果:影响因素及其干预措施包括详解病情及手术风险性;对手术环境及术中情况的告知;完善急诊手术患者家属心理干预;根据不同文化水平进行健康宣教;尽量以病情为主,设计最经济有效的治疗方案;提高医护人员从业技能及道德品质.结论:对等候区手术患者家属进行积极有效的心理干预,可很大程度上减轻患者家属的焦虑程度,缓和医患关系,一定程度上提升了医疗质量. 相似文献
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DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex
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Cheng‐Gen Zhang Shu‐Yuan Yu Liaoyun Zhang Huayi Li Zhi‐Xiang Wang 《Journal of polymer science. Part A, Polymer chemistry》2015,53(4):576-585
DFT computations have been performed to investigate the mechanism of H2‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H2 can react with the deactivated [Zr]?pMS?PPn facilely, which displace functionalized pMS?PPn chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585 相似文献