- A novel synthetic route to pentaalkylcyclopentadienylgallium(I) compounds
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The reaction of 'GaI' with potassium cyclopentadienides allows a simple access to cyclopentadienylgallium(I)-complexes. Thus, the compounds Me5C5Ga 1 and Me4EtC5Ga 2 have been prepared in high yields. Performing the synthesis of 'GaI' under ultrasonic conditions not in toluene but in benzene as solvent, avoids the formation of benzyl iodide as side product.
- Jutzi, Peter,Schebaum, Lars Oliver
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Read Online
- Photoinduced Radical Chain Reactions between Alkylcobalt(III) Complexes and Iodide
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Cobalt-carbon bonds of various alkylcobalt(III) complexes, cis-ClO4 (R=Me, Et, or PhCH2; bipy = 2,2'-bipyridine), trans->CoMe2(L)> (L=3,9-dimethyl-4,8-diazaundeca-3,8-diene-2,10-dione dioximate), and (R=Me or Et; Hdmg = dimet
- Ishikawa, Kunio,Fukuzumi, Shunichi,Goto, Tatsushi,Tanaka, Toshio
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Read Online
- Conversion of Aryl Aldehydes to Benzyl Iodides and Diarylmethanes by H3PO3/I2
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For the first time, H3PO3 was used as both the reducing reagent and the promotor in the reductive benzylation reactions with aryl aldehydes. By using a H3PO3/I2 combination, various aromatic aldehydes underwent iodination reactions and Friedel-Crafts type reactions with arenes via benzyl iodide intermediates, readily producing benzyl iodides and diarylmethanes in good yields. Intramolecular cyclization reactions also took place, giving the corresponding cyclic compounds. This new strategy features easy-handling, low-cost, and metal-free conditions.
- Lv, Fang,Xiao, Jing,Xiang, Junchun,Guo, Fengzhe,Tang, Zi-Long,Han, Li-Biao
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supporting information
p. 3081 - 3088
(2021/02/01)
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- Preparation method of benzyl iodide and derivatives thereof
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The invention discloses a preparation method of benzyl iodide and derivatives thereof, which comprises the following steps: in a protective atmosphere, carrying out heating reaction on aryl aldehyde and iodine elementary substance in the presence of a solvent and phosphorous acid to obtain benzyl iodide and derivatives thereof. According to the method, cheap and green solid phosphorous acid is selected as a reduction reagent for reaction, elemental iodine is selected as an iodine source, the benzyl iodide and the derivatives thereof are efficiently prepared from the aryl aldehyde compounds which are simple and easy to obtain by a one-pot one-step method under mild conditions, and the method has the advantages of simplicity in operation, cheap and easily available reagents, environmental friendliness and the like; and the use of expensive silicon-hydrogen compounds and transition metal catalysts is avoided, and the yield can reach 94% at most, so that the method is beneficial to industrial production.
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Paragraph 0045-0048; 0097-0104
(2021/05/01)
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- Iodine-catalyzed oxidative functionalization of purines with (thio)ethers or methylarenes for the synthesis of purin-8-one analogues
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An efficient oxidative functionalization of purine-like substrates with (thio)ethers or methylarenes under mild conditions is described. Using I2as the catalyst, and TBHP as the oxidant, this protocol provides a valuable synthetic tool for the assembly of a wide range of 9-alkyl(benzyl)purin-8-one derivatives with high atom- and step-economy and exceptional functional group tolerance.
- Zhuge, Juanping,Jiang, Ziyang,Jiang, Wei,Histand, Gary,Lin, Dongen
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supporting information
p. 5121 - 5126
(2021/06/21)
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- Two-Step Protocol for Iodotrimethylsilane-Mediated Deoxy-Functionalization of Alcohols
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We have developed a two-step protocol for iodotrimethylsilane-mediated deoxy-functionalization of primary and secondary alcohols to afford products containing a C?N, C?S, or C?O bond. In the first step the alcohol undergoes iodination with iodotrimethylsilane, and in the second, the iodine atom is replaced by a N, S, or O nucleophile. Compared with traditional Mitsunobu reaction, non-acidic pre-nucleophiles can be used, and the reaction proceeds with retention of configuration. This operationally simple, highly efficient protocol can be used for some natural products and small-molecule drugs containing hydroxy-group.
- Chen, Yuming,He, Ru,Song, Hongjian,Yu, Guoqing,Li, Chenglin,Liu, Yuxiu,Wang, Qingmin
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supporting information
p. 1179 - 1183
(2021/02/01)
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- Iminophosphorane-mediated regioselective umpolung alkylation reaction of α-iminoesters
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Umpolung reactions of imines, especially the asymmetric reactions, have been extensively studied as they provide access to important chiral amines in an efficient manner. The reactions studied range from simple Michael reactions to several kinds of other reactions such as the aza-benzoin reaction, aza-Stetter reaction, addition with MBH carbonate, and Ir-catalysed allylation. Herein, we report the first umpolung alkylation reaction of α-iminoesters with alkyl halides mediated by iminophosphorane as an organic superbase. The desired products were obtained in up to 82% yield with almost perfect regioselectivities. The key to the regioselectivity of this reaction was the use of 4-trifluoromethyl benzyl imines as a substrate. The products were successfully derivatised into the more functionalised molecules in good yields.
- Kukita, Mayu,Mino, Takashi,Omori, Kazuki,Sakamoto, Masami,Yoshida, Yasushi
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p. 4551 - 4564
(2021/05/31)
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- Method for efficiently preparing benzyl iodide and derivatives thereof
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The invention discloses a method for efficiently preparing benzyl iodide and derivatives thereof. The benzyl iodide and the derivatives thereof are prepared by using a benzaldehyde compound as the initial raw material through complex reaction, main reaction and post-reaction. The method specifically includes: placing rhodium and phosphine ligand into a reaction container, adding an organic solvent, stirring for complexing to obtain a reaction system a, adding iodine, stirring under room temperature, adding the initial material benzaldehyde compound to continuously perform stirring reaction toobtain reaction liquid b, transferring into a high-pressure reaction kettle, performing gas replacement, filling hydrogen, keeping positive pressure, performing reaction under room temperature for 4-48 hours to obtain reaction liquid c, and performing vacuum concentration and column chromatography purification to obtain the target benzyl iodide and the derivatives thereof. The method is cheap in used substrate, simple to operate, good in reaction operation safety, environmentally friendly, high in yield, high in the purity of the benzyl iodide and the derivatives thereof, easy to achieve large-scale production and capable of achieving industrial production to satisfy social medical requirements.
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Paragraph 0029-0031
(2020/07/12)
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- Continuous Flow Preparation of (Hetero)benzylic Lithiums via Iodine-Lithium Exchange Reaction under Barbier Conditions
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Herein we report the generation of benzylic lithiums via an iodine-lithium exchange reaction on benzylic iodides performed in continuous flow using tBuLi as the exchange reagent. The resulting benzylic lithium species are trapped in situ by carbonyl electrophiles under Barbier conditions, resulting in benzylic secondary and tertiary alcohols. This flow procedure further allows the generation of highly reactive heterobenzylic lithium compounds, which are difficult to generate under batch conditions. A general scale-up was possible without further optimization.
- Weidmann, Niels,Harenberg, Johannes H.,Knochel, Paul
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supporting information
p. 5895 - 5899
(2020/08/12)
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- The Synthesis of Functionalized 3-Aryl- And 3-Heteroaryloxazolidin-2-ones and Tetrahydro-3-aryl-1,3-oxazin-2-ones via the Iodocyclocarbamation Reaction: Access to Privileged Chemical Structures and Scope and Limitations of the Method
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3-Aryl- and 3-heteroaryloxazolidin-2-ones, by virtue of the diverse pharmacologic activities exhibited by them after subtle changes to their appended substituents, are becoming increasingly important and should be considered privileged chemical structures
- Bell, Abbegail C.,Boomsma, Alex B.,Flikweert, Niecia E.,Hohlman, Robert M.,Zhang, Shiyuan,Blankespoor, Ronald L.,Biros, Shannon M.,Staples, Richard J.,Brickner, Steven J.,Barbachyn, Michael R.
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p. 6323 - 6337
(2020/07/21)
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- Cuprous complex containing diphospho-ortho-carborane ligand as well as preparation method and application thereof (by machine translation)
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The method comprises the following steps, adding :1) solution to the ortho-carborane solution n - BuLi, reacting, at room temperature for 30 - 60min;2), adding, and reacting 1 - 3h;3) with high yield CuI, of the monovalent copper complex to react alcohol and iodide to synthesize the iodo-hydrocarbon 3 - 6h, and synthesizing the iodo-hydrocarbon; through post-treatment at room temperature for synthesizing the iodo-copper complex, by the following steps: reacting the alcohol with the iodide at room temperature and carrying out post-treatment to obtain the monovalent copper complex . The preparation method comprises the following steps: catalyzing alcohol and iodide to react with the iodide, to synthesize the iodo- hydrocarbyl complex; and the method comprises the following steps: catalyzing alcohol and iodide to react. (by machine translation)
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Paragraph 0047-0056
(2020/05/02)
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- Preparation method of benzyl iodide and derivatives thereof
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The invention discloses a preparation method of benzyl iodide and derivatives thereof. The preparation method comprises the following steps: under the reduction action of sodium borohydride, a benzylalcohol compound shown as a formula I reacts with elemental iodine to obtain benzyl iodide shown as a formula II and derivatives thereof; in the formula I and the formula II, R represents one or moresubstituents on a benzene ring and is selected from at least one of aryl, substituted or unsubstituted alkyl, halogen and nitro. The preparation method of benzyl iodide and derivatives thereof is scientific and reasonable, sodium borohydride which is mild in reactivity, low in price and easily available is used as a reducing agent, and elemental iodine is convenient and easily available; in addition, the preparation method has the characteristics of simplicity and convenience in operation, high synthesis yield, easiness in product purification, environmental friendliness and the like.
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Paragraph 0034-0038
(2020/06/09)
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- Method for preparing benzyl iodide and derivatives thereof
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The invention discloses a method for efficiently preparing benzyl iodide and derivatives thereof. The preparation method is characterized in that a benzyl alcohol compound, iodine and hydrogen are used as the reaction raw materials and rhodium and phosphine ligand are used as the catalyst to perform one-step reaction in an organic solvent under a positive pressure condition to synthesize the target benzyl iodide and the derivatives thereof, and the reaction formula of the reaction is as shown in the specification. The method has the advantages that the iodination of the method can be easily achieved, reaction condition requirements are low, large-scale industrial production can be achieved, the yield of the benzyl iodide can reach 82% or above, and the yield of the derivatives of the benzyl iodide can reach 99% or above; the method is wide in application range, short in process flow, low in raw material cost and applicable to the industrial production of a series of benzyl iodide and the derivatives thereof.
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Paragraph 0023-0025
(2020/06/24)
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- Ligand Free Palladium-Catalyzed Synthesis of α-Trifluoromethylacrylic Acids and Related Acrylates by Three-Component Reaction
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Aryl iodides and 2-(trifluoromethyl)acrylic acid reacted together in ligand-free Mizoroki-Heck reaction furnishing a quick and efficient access to highly valuable α-trifluoromethylacrylic acids. The useful transformation was independent with regard to the electronic nature of the aryl group substituent. A three-component one-pot version was also developed to give diverse substituted acrylates. The versatility of α-trifluoromethylacrylic acids was demonstrated by quick access to 3-CF3-coumarins as well as fluorinated analogues of therapeutic or cosmetic agents. Finally, we proposed a catalytic cycle based on the silver carboxylate salt, identified as a key intermediate in the reaction. (Figure presented.).
- Bouillon, Jean-Philippe,Couve-Bonnaire, Samuel,Pannecoucke, Xavier,Xiao, Pan
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supporting information
p. 949 - 954
(2020/01/28)
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- Discovery of Tyrosine Kinase 2 (TYK2) Inhibitor (PF-06826647) for the Treatment of Autoimmune Diseases
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Tyrosine kinase 2 (TYK2) is a member of the JAK kinase family that regulates signal transduction downstream of receptors for the IL-23/IL-12 pathways and type I interferon family, where it pairs with JAK2 or JAK1, respectively. On the basis of human genetic and emerging clinical data, a selective TYK2 inhibitor provides an opportunity to treat autoimmune diseases delivering a potentially differentiated clinical profile compared to currently approved JAK inhibitors. The discovery of an ATP-competitive pyrazolopyrazinyl series of TYK2 inhibitors was accomplished through computational and structurally enabled design starting from a known kinase hinge binding motif. With understanding of PK/PD relationships, a target profile balancing TYK2 potency and selectivity over off-target JAK2 was established. Lead optimization involved modulating potency, selectivity, and ADME properties which led to the identification of the clinical candidate PF-06826647 (22).
- Gerstenberger, Brian S.,Ambler, Catherine,Arnold, Eric P.,Banker, Mary-Ellen,Brown, Matthew F.,Clark, James D.,Dermenci, Alpay,Dowty, Martin E.,Fensome, Andrew,Fish, Susan,Hayward, Matthew M.,Hegen, Martin,Hollingshead, Brett D.,Knafels, John D.,Lin, David W.,Lin, Tsung H.,Owen, Dafydd R.,Saiah, Eddine,Sharma, Raman,Vajdos, Felix F.,Xing, Li,Yang, Xiaojing,Yang, Xin,Wright, Stephen W.
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supporting information
p. 13561 - 13577
(2021/01/01)
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- A general and practical sulfonylation of benzylic ammonium salts with sulfonyl hydrazides for the synthesis of sulfones
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A practical and efficient approach adopting transition-metal-free cross-coupling of sulfonyl hydrazides with benzyl ammonium salts has been developed to synthesize benzyl sulfones using Cs2CO3 as base under mild conditions. The protocol employs stable and easy to handle coupling partners, and is endowed with good substrate compatibility, leading to functional benzyl sulfones in good yields.
- Zhu, Haibo,Zhang, Yingying,Liu, Yishuai,Yang, Liu,Xie, Zongbo,Jiang, Guofang,Le, Zhang-Gao
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- New convergent one pot synthesis of amino benzyl ethers bearing a nitrogen-containing bicycle
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We report herein a new convergent one pot method for the synthesis of amino benzyl ethers containing a bicyclic amine, derived from different substituted benzyl alcohols and bicyclic amino alcohols such as tropine, pseudotropine, and 3-quinuclidinol, using chlorotrimethylsilane and sodium iodide. In order to avoid the competitive reaction with the nitrogen atom, a solution of the separately prepared alkoxide of tropine, pseudotropine, and 3-quinuclidinol was added to the preformed substituted benzyl iodides and allowed to reflux at 90 °C for 15 h under nitrogen atmosphere. This method provides an efficient alternative of the preparation of amino benzyl ethers in organic synthesis with good yields in comparison with existed methods.
- López, Jhon J.,Pérez, Edwin G.
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p. 715 - 723
(2019/02/19)
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- A new HPLC-UV derivatization approach for the determination of potential genotoxic benzyl halides in drug substances
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Benzyl halides, widely used as alkylation reagents in drug synthesis, are potential genotoxic impurities (PGTIs) required to be controlled at trace levels. However, the existing analytical methods for benzyl halides often suffer from matrix interferences or low derivatization efficiency of benzyl chlorides. In this paper, a simple derivatization HPLC-UV method was developed for the analysis of these residual trace benzyl halides in drug substances. 1-(4-Nitrophenyl) piperazine (4-NPP) was selected as a new derivatization reagent because it shifted well the benzyl halides derivatives away to the near visible range (392 nm), which could minimize the matrix interferences from the drug substances and related impurities. Meanwhile, potassium iodide (KI) was used to convert the mixed benzyl halides into benzyl iodides before derivatization. The derivatization parameters were also optimized using the design of experiments (DoE) for achieving the best reaction efficiency. The results showed that the new approach had high specificity and sensitivity, and the LOQs were 7-9 μg g-1 relative to 5 mg mL-1 antipyrine and 17.5-22.5 μg g-1 relative to 2 mg mL-1 oroxylin A. The method is a valuable alternative for the determination of residual benzyl halides in the drug substances.
- Ji, Shunli,Gao, Hongbin,Xia, Xingya,Zheng, Feng
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p. 25797 - 25804
(2019/08/28)
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- I2/Li2CO3-promoted cyanation of diarylalcohols through a dual activation process
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One-step base promoted strategy for cyanation of α,α-diaryl alcohols has been developed under mild and transition metal-free conditions. This method provides a straightforward and facile way towards the synthesis of β,γ-unsaturated nitriles and α-phenylnitiriles from α-vinyl carbinols and α,α-diaryl methanols, respectively, up to 99% yield. Moreover, various azides and ethers could also be accessed from their respective nucleophiles under standard reaction conditions.
- Hu, Liangzhen,Hussain, Muhammad Ijaz,Deng, Qingfu,Liu, Qing,Feng, Yangyang,Zhang, Xiaohui,Xiong, Yan
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supporting information
p. 308 - 314
(2018/12/11)
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- Reaction of the C60 radical anion with alkyl halides
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The reaction of the C60 radical anion (C60-) with α-bromo-1,3-dicarbonyl compounds selectively afforded the methanofullerene derivatives. The reaction with benzyl halide and 1,2-bis(dihalomethyl)benzene afforded the corresponding 1,4-dibenzylated C60 derivative and cycloaddition product, respectively. The possible mechanisms for the formation of the fullerene adducts are proposed.
- Maeda, Yutaka,Sanno, Makoto,Morishita, Tatsunari,Sakamoto, Kodai,Sugiyama, Eiichiro,Akita, Saeka,Yamada, Michio,Suzuki, Mitsuaki
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supporting information
p. 6457 - 6460
(2019/05/10)
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- Rhodium-Catalyzed Generation of Anhydrous Hydrogen Iodide: An Effective Method for the Preparation of Iodoalkanes
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The preparation of anhydrous hydrogen iodide directly from molecular hydrogen and iodine using a rhodium catalyst is reported for the first time. The anhydrous hydrogen iodide generated was proven to be highly active in the transformations of alkenes, phenyl aldehydes, alcohols, and cyclic ethers to the corresponding iodoalkanes. Therefore, the present methodology not only has provided convenient access to anhydrous hydrogen iodide but also offers a practical preparation method for various iodoalkanes in excellent atom economy.
- Zeng, Chaoyuan,Shen, Guoli,Yang, Fan,Chen, Jingchao,Zhang, Xuexin,Gu, Cuiping,Zhou, Yongyun,Fan, Baomin
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supporting information
p. 6859 - 6862
(2018/10/25)
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- Ferric(III) Chloride Catalyzed Halogenation Reaction of Alcohols and Carboxylic Acids Using α,α-Dichlorodiphenylmethane
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A new method for chlorination of alcohols and carboxylic acids, using α,α-dichlorodiphenylmethane as the chlorinating agent and FeCl3 as the catalyst, was developed. The method enables conversions of various alcohols and carboxylic acids to their corresponding alkyl and acyl chlorides in high yields under mild conditions. Particulary interesting is the observation that the respective alkyl bromides and iodides can be generated from alcohols when either LiBr or LiI are present in the reaction mixtures.
- Lee, Chang-Hee,Lee, Soo-Min,Min, Byul-Hana,Kim, Dong-Su,Jun, Chul-Ho
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supporting information
p. 2468 - 2471
(2018/04/25)
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- BBr3-Assisted Preparation of Aromatic Alkyl Bromides from Lignin and Lignin Model Compounds
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For the first time, BBr3-assisted nucleophilic substitution was applied to a variety of β-O-4 and α-O-4 model compounds for the highly effective cleavage of different C-O bonds, including C-Oα-OH, Cβ-O/Cα-O and CMe-O bonds (99% conversion for most cases). Without any pretreatment, the substitution proceeds at room temperature in the absence of any catalyst, or additive, selectively affording phenols and important organic synthesis reagents, aromatic alkyl bromides, in high to excellent yields (up to 98%). Preliminary studies also highlight the prospect of this method for the effective cleavage of different types of C-O bonds in real lignin. A total 14 wt % yield of aromatic alkyl bromide, 4-(1,2-dibromo-3-hydroxypropyl)benzene-1,2-diol (10), has been obtained from an extracted lignin through this method.
- Li, Xuan,He, Jianghua,Zhang, Yuetao
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supporting information
p. 11019 - 11027
(2018/09/06)
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- By nucleophilic substitution reaction to degrade lignin and lignin model compounds (by machine translation)
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The invention through the nucleophilic substitution reaction to degrade lignin and lignin model compound method relates to biomass energy chemical technical field. In order to lignin model compounds and organic solvent-soluble lignin as substrate, to halogenated compound B BX3 As nucleophiles, through the nucleophilic substitution reaction, in - 78 °C to 60 °C conditions, reaction 0.5 h - 36 h, at the same time realize lignin model compound, lignin degradation, and the connection of the X substituent. The operation of the invention the method is simple, mild reaction conditions, not only high conversion and high selectivity (>99% conversion rate, close to 99% [...] selective) realizes the lignin and the degradation of lignin model compound, and obtained the degradation product, is a very high can be modified with the nature contains the bromine compound, can be used as an important organic synthetic intermediates. (by machine translation)
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Paragraph 0050; 0051
(2018/04/03)
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- Production of cyclic carbonate
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The purpose of the present invention is to provide a practical method for producing a cyclic carbonate, which is widely used for various applications such as electrolytic solutions for lithium-ion secondary batteries and plastic materials, by a reaction between an epoxide (oxirane) and carbon dioxide, the method giving consideration to the reduction of environmental loads and making it possible to produce said cyclic carbonate with high yield under mild conditions, such as at room temperature and atmospheric pressure. The present invention relates to a method for producing a cyclic carbonate, the method being characterized by reacting an epoxide and carbon dioxide in the presence of an iodine-anion-containing phosphonium salt including a hydrogen atom that can form a hydrogen bond with an oxygen atom in the epoxide.
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Paragraph 0141
(2017/09/06)
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- Catalytic Halogen Bond Activation in the Benzylic C-H Bond Iodination with Iodohydantoins
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This letter presents the side-chain iodination of electron-deficient benzylic hydrocarbons at rt using N-hydroxyphthalimide (NHPI) as radical initiator and 1,3-diiodo-5,5-dimethylhydantoin and 3-iodo-1,5,5-trimethylhydantoin (3-ITMH) as iodine source. Addition of a carboxylic acid increased the reactivity due to complex formation with and activation of 3-ITMH by proton transfer and halogen bond formation. No SEAr reactions were observed under the employed reaction conditions. Our method enables convenient product isolation and gives 50-72% yields of isolated products.
- Combe, Sascha H.,Hosseini, Abolfazl,Song, Lijuan,Hausmann, Heike,Schreiner, Peter R.
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supporting information
p. 6156 - 6159
(2017/11/24)
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- Oxidant-Triggered C1-Benzylation of Isoquinoline by Iodine-Catalyzed Cross-Dehydrogenative-Coupling with Methylarenes
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A practical iodine-catalyzed oxidative functionalization of isoquinolines with methylarenes is developed, which can be triggered by the selected oxidants to produce C1- or N-benzyl-substituted products selectively. This method utilizes readily available isoquinolines and methylarenes as starting materials and proceeds under metal-free conditions with broad substrate scope with respect to methylarenes, avoiding the usage of expensive metal catalysts and generation of halide and metal wastes.
- Shi, Xin,Zhang, Feng,Luo, Wen-Kun,Yang, Luo
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supporting information
p. 494 - 498
(2017/02/24)
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- Aliphatic C-H Bond Iodination by a N-Iodoamide and Isolation of an Elusive N-Amidyl Radical
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Contrary to C-H chlorination and bromination, the direct iodination of alkanes represents a great challenge. We reveal a new N-iodoamide that is capable of a direct and efficient C-H bond iodination of various cyclic and acyclic alkanes providing iodoalkanes in good yields. This is the first use of N-iodoamide for C-H bond iodination. The method also works well for benzylic C-H bonds, thereby constituting the missing version of the Wohl-Ziegler iodination reaction. Mechanistic details were elucidated by DFT computations, and the N-centered radical derived from the used N-iodoamide, which is the key intermediate in this process, was matrix-isolated in a solid argon matrix and characterized by UV-vis as well as IR spectroscopy.
- Artaryan, Alexander,Mardyukov, Artur,Kulbitski, Kseniya,Avigdori, Idan,Nisnevich, Gennady A.,Schreiner, Peter R.,Gandelman, Mark
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p. 7093 - 7100
(2017/07/26)
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- Selective reaction of benzyl alcohols with HI gas: Iodination, reduction, and indane ring formations
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Reactions of benzyl alcohols with HI in solvent-free conditions were examined. Three types of reactions (iodination, reduction, and ring formation) occurred depending on the degree of crowding around the benzyl position and the benzylic stabilization of substrates. Results also showed that the ring formation to give indanes proceeded efficiently when HI was used, and that compounds with electron-rich aromatic rings gave indane derivatives in good yields.
- Matsumoto, Shoji,Naito, Masafumi,Oseki, Takehisa,Akazome, Motohiro,Otani, Yasuhiko
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p. 7254 - 7259
(2017/11/24)
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- Synthesis method of dialkyl hydrogenated nopyl benzyl quaternary ammonium salt, and antibacterial application thereof
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The invention discloses a method for synthesizing a dialkyl hydrogenated nopyl benzyl quaternary ammonium salt compound, and antibacterial application of the compound. Dialkyl hydrogenated nopyl amine and a benzyl halide are directly subjected to one-step synthesis to obtain dialkyl hydrogenated nopyl benzyl quaternary ammonium salt; in an organic solvent, the dialkyl hydrogenated nopyl amine and the benzyl halide (chlorine, bromine and iodine) are fed into a conical flask according to a material ratio, wherein the conical flask is provided with a stirrer and a condensate backflow device; heating is performed for reaction; the reaction temperature is controlled to be 100 to 150 DEG C; the reaction time is controlled to be 1 to 3d. After reaction, products are subjected to suction filtration, washing, recrystallization and vacuum drying; seven dialkyl hydrogenated nopyl benzyl quaternary ammonium salt compounds are obtained through synthesis; the seven dialkyl hydrogenated nopyl benzyl quaternary ammonium salt compounds have a good inhibition effect on phoma citricarpa and colletorichum glecosporioides. The raw materials are rich; the operation is simple; the reaction is simple; the reaction conditions are mild; the purification post treatment is simple. Compared with a traditional antibacterial agent, the antibacterial compound has the advantages of simple structure, safety, no toxicity, little environment pollution and the like, and has good application prospects.
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Paragraph 0029
(2017/07/15)
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- A mild and highly chemoselective iodination of alcohol using polymer supported DMAP
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The synthesis of organic compounds using polymer supported catalysts and reagents, where the required product is always in solution, has been of great interest in recent years, both in industries and academia especially in pharmaceutical research. Here, a simple and efficient method for conversion of alcohols into their iodides in high yield using polymer supported 4-(Dimethylamino)pyridine (DMAP) is described. Polymer supported DMAP is used in catalytic amount and is recovered and reused several times. Additionally, this method is highly chemoselective. [Figure not available: see fulltext.]
- Das, Diparjun,H Anal, Jasha Momo,Rokhum, Lalthazuala
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p. 1695 - 1701
(2017/03/08)
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- An efficient and selective method for the iodination and bromination of alcohols under mild conditions
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A straightforward and effective procedure for the conversion of a variety of alcohols into the corresponding alkyl iodides and bromides is described using KX/P2O5 (X = I, Br). The reactions were easily carried out in acetonitrile under mild conditions. Using this method, the selective conversion of benzylic alcohols in the presence of aliphatic alcohols was achieved.
- Khazdooz, Leila,Zarei, Amin,Aghaei, Hamidreza,Azizi, Ghobad,Gheisari, Mohammad Mehdi
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p. 168 - 171
(2015/12/30)
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- Synthesis of Fasicularin
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The synthesis of a tricyclic marine alkaloid, fasicularin, was accomplished. Stereoselective synthesis of the aza-spirocyclic BC-ring precursor and ensuing construction of the A-ring with stereocontrolled installation of the C2 hexyl group feature prominently in the synthesis.
- Kaga, Atsushi,Tnay, Ya Lin,Chiba, Shunsuke
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supporting information
p. 3506 - 3508
(2016/07/26)
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- Indoline derivatives a series of structure containing asymmetric squaraine cyanine small molecule and its application
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The invention provides a series of novel asymmetric squarine micromolecules, and an application thereof. By introducing different electricity-rich aromatic units in two ends of a squaric acid four-membered ring as donor units, a series of low narrow-gap asymmetric squarine micromolecule photovoltaic materials are designed and synthesized. The series of the low narrow-gap asymmetric squarine micromolecule photovoltaic materials have strong absorption in visible and near-infrared light regions; absorption spectra cover400-900 nm; and HOMO and LUMO of the series of the low narrow-gap asymmetric squarine micromolecule photovoltaic materials can match well with energy levels of an acceptor material PCBM to obtain a high open-circuit voltage. The compounds have good solubility and film-forming property, so that the compounds can be applied in bulk hetero-junction organic solar cells processed by low-cost solution. Performances of the organic solar cells with asymmetric squaric acid macromolecules as donor materials can reach an open-circuit voltage Voc=0.72-1.05 V, a short-circuit current Jsc=8.80-12.67 mA/cm, a fill factor (FF)=0.38-0.55, and photoelectric conversion efficiency (PCE)=2.41-6.10%.
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Paragraph 0182-0185
(2019/02/02)
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- Uranyl Schiff base complexes as new heterogeneous catalysts for halogen exchange reactions between alkyl halides and elemental halogens
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Mild and effective procedure for the halogen exchange reaction of alkyl halides with elemental iodine and bromine catalyzed with uranyl Schiff base complexes in various aprotic solvents was developed. Corresponding alkyl bromides and iodides were obtained with high yields within 20—70 min. The structures of the target products were confirmed by physical and spectroscopic data.
- Naeimi,Nazifi
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p. 1814 - 1818
(2016/05/11)
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- Pd(II)-catalyzed chelation-assisted cross dehydrogenative coupling between unactivated C(sp3)H bonds in aliphatic amides and benzylic CH bonds in toluene derivatives
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The chelation-assisted cross dehydrogenative coupling of C(sp3)H bonds is achieved by the Pd(II)-catalyzed reaction of aliphatic amides that contain a 5-chloro-8-aminoquinoline moiety as the directing group with toluene derivatives in the presence of heptafluoroisopropyl iodide. A variety of functional groups are tolerated.
- Kubo, Teruhiko,Aihara, Yoshinori,Chatani, Naoto
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supporting information
p. 1365 - 1367
(2015/11/24)
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- PROCESS FOR THE PREPARATION OF N-IODOAMIDES
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The present invention provides new stable crystalline N-iodoamides - 1-iodo- 3,5,5-trimethylhydantoin (1-ITMH) and 3-iodo-4,4-dimethyl-2-oxazolidinone (IDMO). The present invention further provides a process for the preparation of organic iodides using N-iodoamides of this invention and recovery of the amide co-products from waste water.
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Paragraph 00282-00283
(2015/05/26)
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- Application of "click" chemistry in solid phase synthesis of alkyl halides
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A convenient and highly selective microwave assisted procedure for the conversion of allylic, benzylic and aliphatic alcohols to their corresponding halides using polymer-bound triphenylphosphine and iodine is presented. In case of symmetrical diols, mono-iodination product is obtained in very high yield. Additionally, highly regioselective behavior is observed in our procedure. Simplicity in operation, no column chromatography required for the purification of the products, recyclability of the reagents used, short reaction times and good to excellent yields are the advantages of our protocol. Most functional groups remain unaffected under our reaction condition.
- Das, Diparjun,Chanda, Tridib,Rokhum, Lalthazuala
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p. 775 - 783
(2016/01/20)
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- Ruthenium bipyridyl tethered porous organosilica: A versatile, durable and reusable heterogeneous photocatalyst
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A versatile heterogeneous photocatalysis protocol was developed by using ruthenium bipyridyl tethered porous organosilica (Ru-POS). The versatility of the Ru-POS catalyst in organo-photocatalysis was explored by (i) oxidative aromatization of Hantzsch ester, (ii) reductive dehalogenation of alkyl halides, and (iii) functional group interconversion (FGI) of alcohols to alkyl halides. This journal is
- Jana, Avijit,Mondal, John,Borah, Parijat,Mondal, Sujan,Bhaumik, Asim,Zhao, Yanli
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supporting information
p. 10746 - 10749
(2015/06/30)
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- Design, synthesis and anticancer activities of novel otobain derivatives
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A series of novel racemic otobain derivatives was designed and synthesised using 2-piperonyl-1,3-dithianes in the conjugate addition-alkylation to 5H-furan-2-one, followed by cationic cyclisation. All the synthesised compounds were consequently evaluated for their anticancer activity against several human cancers in vitro. The efficacy of the most active compound 27g was comparable with etoposide, with IC50 values ranging from 1.06 μM to 4.16 μM in different cancer cell lines. Notably, compound 27g strongly induced cell cycle arrest and increased the expression of mitosis-specific markers MPM-2 and phosphorylated histone H3, but it did not trigger cell apoptosis. Further a colony formation assay showed that compound 27g effectively inhibited the anchor growth of lung cancer cells in a dose-dependent manner. More importantly, compound 27g at 40 mg kg-1 significantly suppressed tumour volume (P 0.01) and tumour weight (P 0.05) in a human lung cancer cell xenograft mouse model without causing systematic toxicity in mice. Our findings indicated that compound 27g has significant potential for further drug development.
- Li, Zhongzhou,Su, Hui,Yu, Weiwei,Li, Xinjun,Cheng, Hao,Liu, Mingyao,Pang, Xiufeng,Zou, Xinzhuo
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p. 277 - 287
(2015/12/30)
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- MgI2-Mediated Chemoselective Cleavage of Protecting Groups: An Alternative to Conventional Deprotection Methodologies
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The scope of MgI2 as a valuable tool for quantitative and mild chemoselective cleavage of protecting groups is described here. This novel synthetic approach expands the use of protecting groups, widens the concept of orthogonality in synthetic processes, and offers a facile opportunity to release compounds from solid supports. Amazing MgI2: Protecting groups have had a tremendous positive impact on the art of biomolecule synthesis. In a context in which the use of attractive protecting groups is often limited by harsh deprotection conditions and low chemoselective flexibility, MgI2 offers, by the execution of a very simple protocol, a fresh vision with extensive perspectives.
- Berthet, Mathéo,Davanier, Florian,Dujardin, Gilles,Martinez, Jean,Parrot, Isabelle
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supporting information
p. 11014 - 11016
(2015/11/10)
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- One-pot preparation of alkyl iodides from esters by indium-catalyzed reductive cleavage of a carbon-oxygen bond
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We describe the indium-catalyzed reductive iodination of aliphatic and aromatic esters with iodine and 1,1,3,3- tetramethyldisiloxane (TMDS). This reducing procedure accommodates a variety of esters, including esters containing alkyl groups, halogens, a hydroxy group, a thioether, and an alkene moiety. Also, this procedure was applied to the cleavage of carbon-oxygen bonds in acrylate polymers.
- Sakai, Norio,Matsushita, Yohei,Konakahara, Takeo,Ogiwara, Yohei,Hirano, Keisuke
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supporting information
p. 1591 - 1595
(2015/03/04)
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- Potassium iodide-catalyzed three-component synthesis of 2-arylquinazolines via amination of benzylic C-H bonds of methylarenes
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A novel potassium iodide-catalyzed three-component synthesis of quinazolines via benzylic C-H bonds amination was developed. Commonly used ammonia salt and the sp3 carbon in commercially available methylarenes were used as nitrogen and C1 sources, respectively. Mechanistic studies indicated that an aryl aldehyde is involved as a key intermediate in the reaction.
- Zhao, Dan,Shen, Qi,Li, Jian-Xin
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supporting information
p. 339 - 344
(2015/03/04)
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- Manganese(III)-mediated selective diphenylphosphinoyl radical reaction of 1,4-diaryl-1-butynes for the synthesis of 2-phosphinoylated 3,4- dihydronaphathalenes
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A diphenylphosphinoyl radical-initiated sequential reaction of 1,4-diaryl-1-butynes and analogues is developed for the synthesis of 2-phosphinoylated 3,4-dihydronaphathalenes and related compounds.
- Li, Da-Peng,Pan, Xiang-Qiang,An, Li-Tao,Zou, Jian-Ping,Zhang, Wei
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p. 1850 - 1855
(2014/03/21)
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- The synthesis and structure revision of NSC-134754
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The synthesis of emetine analogue NSC-134754, a potent inhibitor of the HIF pathway, has been accomplished and its structure reassigned. The stereochemistry of NSC-134754 has been assigned for the first time using X-ray crystallography and it has been demonstrated that only one diastereoisomer is active against HIF.
- Hickin, Jennie A.,Ahmed, Afshan,Fucke, Katharina,Ashcroft, Margaret,Jones, Keith
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supporting information
p. 1238 - 1240
(2014/01/17)
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- Ionic liquid-induced conversion of methoxymethyl-protected alcohols into nitriles and iodides using [Hmim][NO3]
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This Letter reports a one-pot efficient conversion of methoxymethyl-ethers into their corresponding nitriles and iodides using the ionic liquid, 1-methyl-3H-imidazolium nitrate ([Hmim][NO3]) under microwave irradiation. A variety of products were prepared in high yields using this method.
- Noei, Jalil,Mirjafari, Arsalan
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supporting information
p. 4424 - 4426
(2014/08/05)
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- Indium(III)-catalyzed one-pot synthesis of alkyl cyanides from carboxylic Acids
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The one-pot preparation of alkyl cyanides from carboxylic acids via alkyl iodides or alkyl bromides, which were in situ generated either by indium(III)-catalyzed reductive iodination or bromination of carboxylic acids, is described. Georg Thieme Verlag Stuttgart New York.
- Moriya, Toshimitsu,Shoji, Kohei,Yoneda, Shinichiro,Ikeda, Reiko,Konakahara, Takeo,Sakai, Norio
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p. 3233 - 3238
(2013/12/04)
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- Carbocations generated under stable conditions by ionization of matrix-isolated radicals: The allyl and benzyl cations
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Carbocations are crucial intermediates in many chemical reactions; hence, considerable effort has gone into investigating their structures and properties, for example, in superacids, in salts, or in the gas phase. However, studies of the vibrational structure of carbocations are not abundant, because their infrared spectra are difficult to obtain in superacids or salts (where furthermore the cations may be perturbed by counterions), and the generation of gas-phase carbocations in discharges usually produces several species. We have applied the technique of ionizing neutral compounds by X-irradiation of cryogenic Ar matrices to radicals embedded in such matrices, thus producing closed-shell cations that can be investigated leisurely, and in the absence of counterions or other perturbing effects, by various forms of spectroscopy. This Article describes the first set of results that were obtained by this approach, the IR spectra of the allyl and the benzyl cation. We use the information obtained in this way, together with previously obtained data, to assess the changes in chemical bonding between the allyl and benzyl radicals and cations, respectively.
- Misic, Vladimir,Piech, Krzysztof,Bally, Thomas
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p. 8625 - 8631
(2013/07/25)
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- Expanding the scope of the asymmetric anti-aldol addition of chiral N-amino cyclic carbamate hydrazones
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An asymmetric anti-aldol addition process of ketone-derived donors that is not limited by the structure of the ketone is described. This is achieved by merging the enantioselective α,α-bisalkylation of N-amino cyclic carbamate (ACC) hydrazones with the asymmetric anti-aldol addition of ACC hydrazones. The products of this process are obtained with essentially perfect stereoselectivity. Using this procedure it is possible to gain access to ketone-based anti-aldol addition products that are inaccessible in a controlled sense via direct aldol methods.
- Knight, John D.,Coltart, Don M.
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supporting information
p. 5470 - 5472
(2013/09/23)
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- Asymmetric anti-aldol addition of achiral ketones via chiral N-amino cyclic carbamate hydrazones
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The asymmetric anti-aldol addition of ketone-derived donors and aldehyde acceptors is described. Asymmetric induction is achieved through the use of chiral N-amino cyclic carbamate (ACC) auxiliaries. The transformation exhibits essentially perfect anti-diastereoselectivity and enantioselectivity, and has the unusual feature of proceeding via thermodynamic, rather than kinetic control.
- Knight, John D.,Coltart, Don M.
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supporting information
p. 7495 - 7497
(2013/08/23)
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- Effective and one-step stereo-controlled synthesis of benzyloxylated- diiodopentanes for the synthesis of five-membered imino-sugars
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An effective and stereo-controlled synthesis of 1,3,4-tris(benzyloxy)-2,5- diiodopentane starting from 2,3,5-tris(benzyloxy)pentane-1,4-diol was reported. Synthesis was improved to get the diiodide compound instead of forming the ring-closure product (ben
- Guo, Lina,Liu, Yonghui,Wan, Yue,Wang, Peng George,Zhao, Wei
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p. 2579 - 2582
(2013/06/26)
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- Iodine-mediated thioetherification of alcohols with disulfides or NaSh under microwave irradiation
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An efficient and novel method for the thioetherification of an alcohol with disulfides or NaSH under microwave irradiation is presented. In the presence of iodine, a variety of alcohols were smoothly S-alkylated with disulfides or NaSH to give the corresponding thioethers in moderate to excellent yields. Copyright
- Hu, Bolun,Sun, Leilei,Tang, Riyuan,Hu, Huanan
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p. 2556 - 2562,7
(2020/09/16)
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