Activation of DMSO by Phosphonitrilic Chloride: An Efficient Method for Oxidation of Alcohols

A variety of alcohols have been oxidized under mild conditions by a dimethylsulfoxide (DMSO)–chlorophosphazene complex. Sensitive groups such as silyl and tetrahydropyranyl (THP) ethers are stable under this condition.     

An Efficient Method for the Oxidation of Urazoles Under Mild and Heterogeneous Conditions

A combination of inorganic acidic salts or silica gelsupported inorganic acids and sodium nitrite in the presence of wet SiO₂ was used as an effective oxidizing agent for the oxidation of urazoles and bis-urazoles to their corresponding triazolinediones under mild and heterogenous conditions in good yields. Silica gel supported nitric acid and ceric ammonium nitrate (CAN) are also capable of effecting these oxidations in the absence of sodium nitrite in moderate to good yields. Mg(HSO₄)₂ is a superior to all the aforementioned reagents in convenience, yield and purity of the isolated triazolinediones.     

An Efficient Method for the Synthesis of Laquinimod

Laquinimod, 5‐chloro‐1,2‐dihydro‐N‐ethyl‐4‐hydroxy‐1‐methyl‐2‐oxo‐N‐ phenyl‐3‐quinoline carboxamide, is an oral drug in clinical trials for the treatment of multiple sclerosis. An efficient synthetic method for laquinimod from 2‐amino‐6‐chlorobenzoic acid via four steps was established. The overall yield of laquinimod is up to 82% as compared with 70% reported in literature. It has also been demonstrated that green reagent dimethyl carbonate is not suitable for the N‐methylation of 5‐chloroisatoic anhydride owing to the ring‐cleavage reaction induced by the generated methanol. The ring‐cleavage by‐products were isolated and characterized by ¹H‐NMR and ¹³C‐NMR. In addition, in the study of laquinimod derivatives, we found that 5‐chloro‐1,2‐dihydro‐N‐ethyl‐4‐hydroxy‐1‐methyl‐2‐oxo‐N‐phenyl‐3‐quinoline carboxamide (laquinimod) was obtained in much higher yield than 7‐chloro‐1,2‐dihydro‐N‐ethyl‐4‐hydroxy‐1‐methyl‐2‐oxo‐N‐phenyl‐3‐quinoline carboxamide under the same reaction conditions, and it is possibly attributed to a neighboring group effect.     

Double Cycloadditive Macrocyclization: An Efficient Method for Cyclophane

A series of macrocycles containing isoxazoline and [1,4,2]dioxazole were synthesized for the first time. The structures of the newly synthesized macrocycles were characterized and confirmed by IR, ¹H NMR, mass spectra, and elemental analysis. The solid‐state structure of macrocycle ( 6d ) was further studied by single‐crystal X‐ray diffraction analysis.     

An Efficient Method for the Reduction of Cephalosporin Sulfoxides

An efficient and convenient method for the reduction of cephalosporin sulfoxides to their corresponding sulfides by Lawesson reagent is reported.     

An Efficient Method for the Synthesis of 1-Arylalkynes

1-Arylalkynes are prepared from propiophenones in good yield via the sequence a) 2 equiv PCl₅/Δ b) DBN or Δ and c) Mg metal.     

Polymer Supported Reagents: An Efficient Method for the Synthesis of Diaryloxymethanes

Diaryloxymethanes were synthesized in high yield and in high purity by the treatment of polymer supported phenoxide ions with dichloromethane.     

氮氧自由基TEMPO：选择氧化醇的高效有机小分子催化剂*

醇被氧化为相应的醛或酮是有机合成中重要的官能团转换反应之一。自从Anelli法（TEMPO/NaBr/NaOCl）发现以来,由于所具有的醇被氧化为相应的醛或酮是有机合成中重要的官能团转换反应之一。自从Anelli法（TEMPO/NaBr/NaOCl）发现以来,由于所具有的高活性和高选择性, 有机小分子催化剂2,2,6,6-四甲基哌啶-1-氧自由基(TEMPO)催化醇的氧化反应成为温和条件下醇选择氧化的一个重要方法,并在实验室和工业生产中广泛应用。最近有关TEMPO催化醇氧化反应的研究,主要集中在开发用于分子氧对醇绿色氧化的催化体系和目的在于实现催化剂回收再用的TEMPO固载化研究两个领域上。本文以此为重点,综述了TEMPO催化醇氧化反应的发展和最近研究进展。     

An Efficient,Simple and Inexpensive Method for the Preparation of 1,4-Benzoquinone Monoketals via Anodic Oxidation of 1,4-Dimethoxybenzenes

Anodic oxidation of a series of 1-substituted-2,5-dimethoxybenzenes gives 2-substituted-1,1,4,4-tetramethoxycyclohexa-2,5-dienes in almost quantitative crude yield. Selective monohydrolysis of these bis-ketals is possible in many cases, and gives 3-substituted-4,4-dimethoxycyclohexa-2,5-dienones in good to excellent overall yield.     

An Efficient Method for the Oxidation of Hantzsch 1,4-Dihydropyridines to their Corresponding Pyridine Derivatives Under Mild and Heterogeneous Conditions

A combination of oxalic acid dihydrate and sodium nitrite in the presence of wet SiO₂ was used as an effective oxidizing agent for the oxidation of dihydropyridines to their corresponding pyridine derivatives at room temperature with excellent yields.     

An Efficient Method for Synthesis of Tofacitinib Citrate

An efficient and mild synthetic method was developed for tofacitinib citrate from 3‐amino‐4‐methylpyridine and 4‐chloro‐7H‐pyrrolo[2,3‐d]pyrimidine. The related reactions were systematically optimized. Sodium hydride instead of potassium tert‐butoxide employed in the methoxycarbonylation reaction of compound 9 made the reaction proceed effectively to present compound 8 in a better yield. The replacement of benzaldehyde with benzyl bromide simplified the protection process of amino group. Red‐Al provided a cost‐effective method for the reduction of amides. The introduction of tosyl group into compound 10 enhanced the nucleophilic substitution of 10 with compound 4 dramatically. Thus, under the optimized conditions, tofacitinib citrate was obtained in 13.3% yield (based on compound 9 ) with a purity of 99.9%, much better than the reported yield 8.6%. This cost‐effective and environmental friendly process is more suitable for scale‐up production.     

An Efficient Method for the Programmed Synthesis of Multifunctional Diketopyrrolopyrroles

A new, transformative methodology for the preparation of diketopyrrolopyrroles from aldehydes, primary amines, nitriles, and diethyl oxalacetate has been developed. It is now possible to prepare diketopyrrolopyrroles bearing an ordered arrangement of three different substituents from abundant and commercially available materials, allowing the independent regulation of all desired physicochemical properties. For the first time very electron‐rich (carbazol‐3‐yl, dimethylaminophenyl, pyrrolo[3,2‐b]pyrrolyl), and sterically hindered substituents (naphthalen‐1‐yl, quinolin‐4‐yl, acridin‐9‐yl, imidazo[1,5‐a]pyridin‐1‐yl, 2‐bromophenyl etc.) can be appended to the diketopyrrolopyrrole core by condensation of an appropriate nitrile with a pyrrolidin‐2‐one intermediate. Even greater synthetic possibilities are related to the fact that such demanding substituents as 4‐dimethylaminophenyl, indol‐3‐yl, and 2‐methoxyphenyl can be incorporated from aldehyde precursors, bypassing problems with the nitriles reactivity.     

An Efficient Solid-Phase Method for the Preparation of Diaryl Carbazones

The preparation of diaryl carbazones on solid-phase is reported for the first time. Using Fe(NO₃)₃.9H₂O as oxidant, seven diaryl carbazones have been synthesized under mild conditions in excellent yields. The method is convenient and efficient.     

一种有效的从五氟氯乙烷合成五氟碘乙烷的方法

本文发展了一种有效的从五氟氯乙烷合成五氟碘乙烷的方法。仔细考察了五氟氯乙烷亚磺化脱氯的条件,由此生成的五氟乙基亚磺酸盐无须纯化,可以直接进行碘化,能以中等收率生成相应的五氟碘乙烷。     

神经节苷脂GM3的有效合成

报道了α-Neu5Ac-(2-3)-β-Gal-(1-4)-β-Glc-(1-1)-Cer (GM3)的有效合成方法. 将选择性保护的乳糖二醇与唾液酸黄原酸酯(Xanthate)在AgOTf/PhSCl催化下高立体、高区域选择性糖苷化得到含唾液酸的三糖, 经脱苄基保护及全乙酰化后, 在温和条件下脱去还原端保护基, 并制备成三氯乙酰亚胺酯糖苷, 与选择性保护的鞘氨醇缩合得到含叠氮化合物9. 后者用Ph₃P还原后, 在EDC存在下与硬脂酸酰化反应, 得化合物11, 脱去保护基后获得目标产物GM3 (1), 为研究肿瘤疫苗提供有用材料. 化合物结构经NMR, MS和HRMS确证.     

An Efficient Method for α-Alkylation of γ-Butyrolactone

Alkylated lactone is a common structure and segment in many natural products and medicines. The examples of alkylating lactone system at -position, obtained by reaction with alkyl halide such as MeI, in the presence of strong base LDA or it抯 derivatives, are very few1a, 1b. When this method was applied to the aromatic compound, the self-condensation of g-butyrolactone could not be avoided. In our previous work we have reported the hydrogenation of ? -unsaturated carbonyl compounds by cat…