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在选择性氧化的研究中,Cr(Ⅵ)类选择性氧化剂都存在着需特殊制备、配体和溶剂昂贵等缺点。同时,相转移催化技术的使用,也使许多氧化剂有了较好的选择性,但对环境污染严重。间接电氧化虽没有用量大、污染严重的缺点,但没有选择性。为此,我们使用间接电氧化和相转移催化氧化联用的方法,克服了上述缺点。并用Cr(Ⅵ)/Cr(Ⅲ)为间接氧化还原体系对醇类的选择性氧化进行了探讨。结果发现,本实验条件下,苄醇类会选择性地氧化成相应的羰基化合物,且产率高,而非苄醇类的醇则达不到此目的。 相似文献
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相转移催化下肟类的选择性间接电氧化研究 总被引:1,自引:0,他引:1
以Ce^4+/Ce^3+为间接电氧化还原体系,在相转移催化剂PhCH2N(C2H5)3Cl存在下,对肟类化合物进行选择性间接电氧化。结果表明,在室温条件下,电解2h,肟类能被选择性地氧化为相应的羰基化合物,收率75-95.6%。 相似文献
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相转移催化下Mn(Ⅲ)/Mn(Ⅱ)体系对醇类的选择性电氧化 总被引:2,自引:0,他引:2
以Mn(Ⅲ)/Mn(Ⅱ)为间接氧化还原体系,用间接电氧化的方法,在相转移催化条件下对醇类的氧化进行了研究。结果表明,在所用实验条件下,Mn(Ⅲ)可以方便地在电极上生成及再生,对苄醇类及二级脂肪醇类能高产率地选择性氧化成相应的羰基化合物。 相似文献
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以2,2,6,6-四甲基哌啶氮氧自由基(TEMPO)为电催化氧化媒介,六甲基二硅胺烷(HMDS)为氮源,在室温下实现了一锅法电氧化醇类化合物为腈类化合物.采用循环伏安法和电化学原位红外光谱技术分别对TEMPO的电催化性能和一锅法电氧化历程进行了研究.在优化条件下,将该反应体系拓展到系列醇类化合物的电催化氧化中,结果表明,不同的醇类化合物,特别是苄醇,取得了较好的反应收率.基于以上研究结果提出了可能的反应机理. 相似文献
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Yamamoto等曾报道烯丙基型的锡有机化合物可与羰基化合物进行亲核加成反应,得到高烯丙基型的醇.他们还发现此反应具有立体选择性.此后又发现这个反应可以被溶剂中的微量水所催化,使反应加速进行.这些结果促使我们进一步探讨当醛分子中含有羟基、酚基、硝基、卤素等各种不同的反应活性基团时,与烯丙基锡进行的反应.希望找到一种用传统的Grignard试剂无法直接进行的烯丙基化反应. 我们选择了间和邻羟基苯甲醛、间和对硝基苯甲醛、对溴苯甲醛、7-羟基-3,7-二甲基辛醛等化合物作反应底物,在金属锡粉存在下使羰基化合物与烯丙基溴反应.结果都得到了相应的高烯丙基醇. 相似文献
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A mild and efficient method to selectively oxidize chiral sec-1,2-diols has been developed, which demonstrates that 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) can selectively oxidize benzylic or allylic hydroxyl group of sec-1,2-diols under ultrasound wave promotion. The configuration of the adjacent chiral center is retained. 相似文献
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Sodium hypochlorite, a cheap and readily available compound, when supported on silica gel can selectively oxidize benzylic and allylic alcohols to their carbonyl compounds in the presence of catalytic amount of DMSO. 相似文献
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Alexey Y. Koposov 《Tetrahedron letters》2004,45(13):2719-2721
Amides of 2-iodoxybenzenesulfonic acid were prepared by the dioxirane oxidation of the corresponding 2-iodobenzenesulfamides and isolated as stable, microcrystalline products. These new representatives of the pseudocyclic hypervalent iodine compounds can selectively oxidize benzylic alcohols to aldehydes. 相似文献
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Susanne Striegler 《Tetrahedron》2006,62(39):9109-9114
A sugar-discriminating dinuclear copper(II) complex was investigated for its ability to promote aerobic oxidation of primary benzylic alcohols in the presence of TEMPO and base. The transformation of benzyl alcohol to benzaldehyde was chosen as exploratory model reaction. The constitution of the catalytically active species was deducted from isothermal titration calorimetry and kinetic experiments, and the catalytic reaction was characterized both in aqueous organic and aqueous solution. The dinuclear complex is found to selectively oxidize primary over secondary alcohols in aqueous solution at ambient temperature with a turnover rate of 9 h−1. A mechanism for the catalytic cycle is proposed. 相似文献
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Sulfated tungstate was found to be an effective heterogeneous and reusable catalyst for hydroxy group activation–mediated preparation of benzylic ethers including p-methoxybenzylic ethers of a wide range of alcohols and phenols under mild reaction conditions. 相似文献
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2,2,6,6-Tetramethyl-1-piperidinyloxy catalyzes efficient oxidation of primary alcohols to aldehydes by N-chlorosuccinimide, in a biphasic dichloromethane-aqueous pH 8.6 buffer system in the presence of tetrabutylammonium chloride. Aliphatic, benzylic, and allylic alcohols are readily oxidized with no overoxidation to carboxylic acids. Secondary alcohols are oxidized to ketones with a much lower efficiency. Very high chemoselectivities are observed when primary alcohols are oxidized in the presence of secondary ones. Primary-secondary diols are selectively transformed into hydroxy aldehydes, with, in some cases, no detectable formation of the isomeric keto alcohols. 相似文献
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Tian-Sheng Chen Hao Long Yuxing Gao Hai-Chao Xu 《Angewandte Chemie (International ed. in English)》2023,62(40):e202310138
The selective oxygenation of ubiquitous C(sp3)−H bonds remains a highly sought-after method in both academia and the chemical industry for constructing functionalized organic molecules. However, it is extremely challenging to selectively oxidize a certain C(sp3)−H bond to afford alcohols due to the presence of multiple C(sp3)−H bonds with similar strength and steric environment in organic molecules, and the alcohol products being prone to further oxidation. Herein, we present a practical and cost-efficient electrochemical method for the highly selective monooxygenation of benzylic C(sp3)−H bonds using continuous flow reactors. The electrochemical reactions produce trifluoroacetate esters that are resistant to further oxidation but undergo facile hydrolysis during aqueous workup to form benzylic alcohols. The method exhibits a broad scope and exceptional site selectivity and requires no catalysts or chemical oxidants. Furthermore, the electrochemical method demonstrates excellent scalability by producing 115 g of one of the alcohol products. The high site selectivity of the electrochemical method originates from its unique mechanism to cleave benzylic C(sp3)−H bonds through sequential electron/proton transfer, rather than the commonly employed hydrogen atom transfer (HAT). 相似文献
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Tanay Kesharwani 《Tetrahedron》2008,64(26):6090-6102
A procedure for benzylic C-H activation has been developed using a palladium 1,4-aryl to benzylic migration as a key step. Carboxylates and phenoxides readily trap the resulting benzylic palladium intermediates obtained from palladium ‘through space’ migration. Aryl bromides and iodides have been successfully employed in this reaction, furnishing moderate to good yields. The mechanism of this reaction has been studied by deuterium-labeling experiments, which suggest that the migration of palladium from an aryl to a benzylic position occurs reversibly. The reaction conditions developed for the migration process also oxidize the neighboring benzylic alcohols to the corresponding aldehydes and ketones. 相似文献
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2‐Methylphenyl ketones undergo site‐selective acylation at the benzylic position when treated with acid anhydride under UV irradiation in the presence of a palladium catalyst. The benzoyl carbonyl group serves as the photo‐directing group so that the ortho benzylic C?H bond is activated site‐selectively. 相似文献