共查询到19条相似文献,搜索用时 156 毫秒
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研究报道了Au(I)/手性叔胺串联催化实现的一锅法不对称反应,实现从重氮氧化吲哚和氟代烯醇硅醚出发构建螺环季碳氧化吲哚.反应的第一步是3.0 mol% IPrAuBF4催化的重氮氧化吲哚与单氟烯醇硅醚的交叉偶联反应,现场产生N-Ac保护的3-烯基氧化吲哚在手性叔胺-四方酸C1的催化下与N-Ts邻氨基查尔酮再发生不对称Michael/Michael反应,以中等到良好的产率以及对映选择性,>20:1的非对映选择性得到螺环季碳氧化吲哚.反应的关键一步是Au(I)催化的给体-受体类重氮化合物与三取代单氟烯醇硅醚的成烯化反应,高效构建三取代烯烃. 相似文献
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研究利用分子筛、Nafion薄膜、低密度聚乙烯薄膜和囊泡作为微反应器控制有机光化学反应的方向,提高反应的选择性和可能性.在NaY沸石或低密度聚乙烯薄膜中,带有长烷基链或醚链的二芳基化合物光二聚只生成分子内的加成产物,而不生成分子间的加成产物,从而在底物浓度很大的情况下,高选择性地合成了大环化合物.通过控制底物和敏化剂分子在ZSM-5沸石、Nafion薄膜和囊泡中的分布高选择性地控制烯烃光敏氧化反应的方向,单一地生成单重态氧的氧化产物或超氧负离子的氧化产物.利用Nafion薄膜作为介质进行光诱导电子转移,得到超长寿命的电荷分离态. 相似文献
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《中国科学:化学》2017,(3)
本文运用密度泛函理论(DFT)计算,研究了Ni(0)催化炔烃与醛分子间还原偶联反应的机理,确定了该反应最优反应路径是氧化环化、转金属以及还原消除.计算结果表明,无论使用IMes还是SIPr作为配体,反应的区域选择性都由氧化环化步控制;而硅烷的转金属化是整个反应的决速步.这不同于以往对Ni(0)催化炔醛还原偶联反应的理论研究.理论计算表明,当使用IMes作为配体时,主要产物为2-甲基-3-苯基烯丙基硅醚;当使用SIPr作为配体时,主产物则是3-甲基-2-苯基烯丙基硅醚.无论从主产物还是区域选择性,本文的计算结果都与实验报道一致.本文使用反应路径形变-结合能模型研究了IMes作为配体时的区域选择性.结果表明,形成主产物时具有较低的形变能.也就是说,过渡态中炔烃部分与苯基折叠程度较小,共轭程度更大,因此主产物为2-甲基-3-苯基烯丙基硅醚.本课题组还使用2D投影图模型研究了空间效应对不同配体的影响.结果表明,当使用IMes配体时,由于配体体积较小,可以容纳苯基在其周围,从而减小了炔烃上的苯基与醛上苯基的排斥;而使用大位阻的SIPr作为配体时,配体与炔烃上的苯基排斥很大,从而不利于2-甲基-3-苯基烯丙基硅醚的生成. 相似文献
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Two methods including NBS/AgNO3 system and MCPBA oxidation have been developed for the selective oxidations of the exo‐cyclic double bond of spiroacetal enol ethers 2 with multi reactive sites into spiro‐pyanones 3 and 4 . In addition, possible mechanisms for these conversions are proposed. 相似文献
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The oxidation of alkylarenes by dioxygen in the presence of complexes of nickel and cobalt with macrocyclic ethers 18-crown-6
and 15-crown-5 was studied. The conditions for selective catalytic oxidation of ethylbenzene to α-phenylethyl hydroperoxide
were determined. The kinetics of the accumulation of all oxidation products was studied. The order of the formation of the
products at different stages of chain oxidation was determined. The activity of the complexes at the elementary stages of
the chain oxidation of ethylbenzene is discussed.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 689–693, April. 1997. 相似文献
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TEMPO‐Mediated oxidation of hydroxylamines (=hydroxyamines) and alkoxyamines to the corresponding oxime derivatives is reported (TEMPO=2,2,6,6‐tetramethylpiperidin‐1‐yloxy radical; Scheme 2). These environmentally benign oxidations proceed in good to excellent yields (Table 1). For alkoxyamines, oxidation to the corresponding oxime ethers can be performed by using dioxygen as a terminal oxidant in the presence of 5–10 mol‐% of TEMPO or 4‐substituted derivatives thereof as a catalyst (Scheme 3 and Table 2). Importantly, benzyl bromides can directly be transformed to oxime ethers via in situ alkoxyamine formation by a nucleophilic substitution followed by TEMPO‐mediated oxidation (Scheme 4 and Table 3). 相似文献
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Yoshihiro Kon 《Tetrahedron letters》2011,52(50):6739-6742
The selective hydrogen peroxide oxidation of vinyl ethers to give acetates was developed using triphenylphosphine palladium and triethyl amine catalysts under mild reaction conditions. 相似文献
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Summary The major cyclic ethers formed in the cool flame oxidation of reference fuels (normal heptane, isooctane, and normal decane) have been identified by gas chromatography-mass spectrometry. The spectra obtained by electronic ionization are presented. Since these ethers are not available commercially and their mass spectra are missing from standard mass spectrometry libraries the present mass spectra could be used as references in future work. 相似文献
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WANG Gui-Xiu ZHU Rong-Xiu ZHANG Dong-Ju② LIU Cheng-Bu 《结构化学》2006,25(11):1402-1408
1 INTRODUCTION Ethers are a kind of organic compounds that are easily oxidized under the conditions of lacking light and any additional excitement. According to dif- ferent mechanisms, the oxidation reactions could be classified into two types: photooxidation reaction and dark oxidation reaction. The former is the reaction with excited state oxygen molecule (singlet state), while the latter is the reaction with ground state oxygen molecule (triple state) without illuminance or any exciter… 相似文献
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An efficient and practical synthesis of dissymmetrical ethers of 4-nitrocatechol from 5-nitrosalicyladehyde and 2-hydroxy-5-nitroacetophenone via Baeyer–Villiger oxidation is described. These dissymmetrical ethers are useful in the synthesis of various coccidiostats and other important pharmaceutical intermediates. 相似文献
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Trinitratocerium(IV) bromate (TNCB) can be used as an efficient reagent for oxidation of alcohols and deprotection and oxidative deprotection of trimethylsilyl ethers under solvent‐free conditions. 相似文献