- Chromenes involving a two-photon absorbing moiety: Photochromism via intramolecular resonance energy transfer
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New derivatives involving the photochromic 2H-benzo[h]chromene moieties covalently linked to the 2,7-bis(carbazolyl)fluorene-derived two-photon absorbing moiety were designed to enable the possibility of resonance energy transfer from the fluorene donor to the photochromic acceptor. The longest wavelength absorption of the photochromic acceptors overlaps with the fluorescence band of the two-photon absorbing donor and the distance between the both moieties is about 5-7 ?. Rapid coloration of colorless solutions was observed upon one- and two-photon absorption.
- Bekere, Laura,Lokshin, Vladimir,Sigalov, Mark,Gvishi, Raz,Zhao, Peng,Hagan, David J.,Van Stryland, Eric W.,Khodorkovsky, Vladimir
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Read Online
- Iridium-Catalyzed Hydroiodination and Formal Hydroamination of Olefins with N-Iodo Reagents and Molecular Hydrogen: An Umpolung Strategy
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We herein report a convenient method to convert olefins to organic iodides and amines using an Ir/ZhaoPhos catalyst, molecular hydrogen, and an electrophilic iodine(I) reagent. High yields and regioselectivities were obtained under mild conditions. In addition, basic workup with potassium carbonate leads to C-N products. Control experiments and DFT calculations tentatively excluded the pathway involving the in situ formation of HI. Instead, a catalytic cycle involving the hydrogenation of the haliranium ion intermediate was proposed.
- Wen, Jialin,Yang, Huaxin,Zhang, Xumu,Zhang, Zhihan,Zhou, Yang
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supporting information
p. 1842 - 1847
(2022/03/14)
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- One-Pot Deoxygenation and Substitution of Alcohols Mediated by Sulfuryl Fluoride
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Sulfuryl fluoride is a valuable reagent for the one-pot activation and derivatization of aliphatic alcohols, but the highly reactive alkyl fluorosulfate intermediates limit both the types of reactions that can be accessed as well as the scope. Herein, we report the SO2F2-mediated alcohol substitution and deoxygenation method that relies on the conversion of fluorosulfates to alkyl halide intermediates. This strategy allows the expansion of SO2F2-mediated one-pot processes to include radical reactions, where the alkyl halides can also be exploited in the one-pot deoxygenation of primary alcohols under mild conditions (52-95% yield). This strategy can also enhance the scope of substitutions to nucleophiles that are previously incompatible with one-pot SO2F2-mediated alcohol activation and enables substitution of primary and secondary alcohols in 54-95% yield. Chiral secondary alcohols undergo a highly stereospecific (90-98% ee) double nucleophilic displacement with an overall retention of configuration.
- Epifanov, Maxim,Mo, Jia Yi,Dubois, Rudy,Yu, Hao,Sammis, Glenn M.
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p. 3768 - 3777
(2021/03/01)
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- Copper-Catalyzed Alkoxycarbonylation of Alkyl Iodides for the Synthesis of Aliphatic Esters: Hydrogen Makes the Difference
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A copper-catalyzed alkoxycarbonylation transformation of unactivated alkyl iodides has been developed. Various alkyl iodides can be converted into the corresponding tert-butyl esters in good yields. NaOtBu acts as both a nucleophile and a base. Moreover, other types of aliphatic esters can also be obtained in moderated yields if extra alcohols are added. Both primary and secondary alkyl alcohols can react successfully.
- Geng, Hui-Qing,Wu, Xiao-Feng
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supporting information
p. 8062 - 8066
(2021/10/25)
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- A click-based modular approach to introduction of peroxides onto molecules and nanostructures
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Copper-promoted azide/alkyne cycloadditions (CuAAC) are explored as a tool for modular introduction of peroxides onto molecules and nanomaterials. Dialkyl peroxide-substituted alkynes undergo Cu(i)-promoted reaction with azides in either organic or biphas
- Dussault, Patrick H.,Horn, Alissa
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p. 44408 - 44429
(2020/12/28)
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- Migratory Hydrogenation of Terminal Alkynes by Base/Cobalt Relay Catalysis
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Migratory functionalization of alkenes has emerged as a powerful strategy to achieve functionalization at a distal position to the original reactive site on a hydrocarbon chain. However, an analogous protocol for alkyne substrates is yet to be developed. Herein, a base and cobalt relay catalytic process for the selective synthesis of (Z)-2-alkenes and conjugated E alkenes by migratory hydrogenation of terminal alkynes is disclosed. Mechanistic studies support a relay catalytic process involving a sequential base-catalyzed isomerization of terminal alkynes and cobalt-catalyzed hydrogenation of either 2-alkynes or conjugated diene intermediates. Notably, this practical non-noble metal catalytic system enables efficient control of the chemo-, regio-, and stereoselectivity of this transformation.
- Liu, Bingxue,Liu, Qiang,Liu, Xufang
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supporting information
p. 6750 - 6755
(2020/03/13)
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- Nickel-Catalyzed Formal Aminocarbonylation of Unactivated Alkyl Iodides with Isocyanides
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Herein, we disclose a Ni-catalyzed formal aminocarbonylation of primary and secondary unactivated aliphatic iodides with isocyanides to afford alkyl amide, which proceeds via the selective monomigratory insertion of isocyanides with alkyl iodides, subsequent β-hydride elimination, and hydrolysis process. The reaction features wide functional group tolerance under mild conditions. Additionally, the selective, one-pot hydrolysis of reaction mixture under acid conditions allows for expedient synthesis of the corresponding alkyl carboxylic acid.
- Chen, Yifeng,Huang, Wenyi,Qu, Jingping,Shrestha, Mohini,Wang, Yun,Weng, Yangyang
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supporting information
p. 3245 - 3250
(2020/04/21)
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- Photochemical Decarboxylative C(sp3)-X Coupling Facilitated by Weak Interaction of N-Heterocyclic Carbene
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While N-hydroxyphthalimide (NHPI) ester has emerged as a powerful reagent as an alkyl radical source for a variety of C-C bond formations, the corresponding C(sp3)-N bond formation is still in its infancy. We demonstrate herein transition-metal-free decarboxylative C(sp3)-X bond formation enabled by the photochemical activity of the NHPI ester-NaI-NHC complex, giving primary C(sp3)-(N)phth, secondary C(sp3)-I, or tertiary C(sp3)-(meta C)phth coupling products. The primary C(sp3)-(N)phth coupling offers convenient access to primary amines.
- Chen, Kun-Quan,Wang, Zhi-Xiang,Chen, Xiang-Yu
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supporting information
p. 8059 - 8064
(2020/11/02)
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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 0047-0049; 0052-0056
(2020/05/02)
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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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- Alkyl Group Migration in Ni-Catalyzed Conjunctive Coupling with C(sp3) Electrophiles: Reaction Development and Application to Targets of Interest
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A catalytic conjunctive cross-coupling reaction is developed that allows the construction of chiral organoboronic esters from alkylboron ate complexes and alkyl iodide electrophiles. The process occurs most efficiently with a Ni/Pybox-comprised catalyst a
- Koo, Seung Moh,Vendola, Alex J.,Momm, Sarah Noemi,Morken, James P.
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supporting information
p. 666 - 669
(2020/01/31)
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- Aryl Substituted Benzimidazolones as Potent HIV-1 Non-Nucleoside Reverse Transcriptase Inhibitors
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Since the discovery of HIV as the etiological agent of AIDS, the virus has infected millions of people each year. Fortunately, with the use of HAART, viremia can be suppressed to below detectable levels in the infected individuals, which significantly improves their quality of life and prevents the onset of AIDS. However, HAART is not curative and issues relating to adherence and drug resistance may lead to the re-emergence of viremia, the development of AIDS, and ultimately death. To address a pressing need for the development of new and efficacious antiretroviral agents with activity against viruses bearing prevalent resistant mutations, we have designed two generations of benzimidazolone derivatives as HIV non-nucleoside reverse transcriptase inhibitors. The first generation benzimidazolone inhibitors were found to be potent inhibitors of wild-type HIV reverse transcriptase but were ineffective in the presence of common resistance mutations such as K103N and Y181C. A second generation benzimidazolone inhibitor (compound 42) not only showed inhibitory activity against wild-type HIV but also remained active against HIV containing the K103N, Y181C, and K103N/Y181C drug resistance mutations.
- Pribut, Nicole,Basson, Adriaan E.,Van Otterlo, Willem A. L.,Liotta, Dennis C.,Pelly, Stephen C.
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supporting information
p. 196 - 202
(2019/02/05)
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- Nucleophilic Substitution of Aliphatic Fluorides via Pseudohalide Intermediates
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A method for aliphatic fluoride functionalization with a variety of nucleophiles has been reported. Carbon–fluoride bond cleavage is thermodynamically driven by the use of silylated pseudohalides TMS-OMs or TMS-NTf2, resulting in the formation of TMS-F and a trapped aliphatic pseudohalide intermediate. The rate of fluoride/pseudohalide exchange and the stability of this intermediate are such that little rearrangement is observed for terminal fluoride positions in linear aliphatic fluorides. The ability to convert organofluoride positions into pseudohalide groups allows facile nucleophilic attack by a wide range of nucleophiles. The late introduction of the nucleophiles also allows for a wide range of functional-group tolerance in the coupling partners. Selective alkyl fluoride mesylation is observed in the presence of other alkyl halides, allowing for orthogonal synthetic strategies.
- Jaiswal, Amit K.,Prasad, Pragati K.,Young, Rowan D.
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p. 6290 - 6294
(2019/04/26)
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- Stereospecific Synthesis of E-Alkenes through Anti-Markovnikov Hydroalkylation of Terminal Alkynes
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We have developed a method for stereospecific synthesis of E-alkenes from terminal alkynes and alkyl iodides. The hydroalkylation reaction is enabled by a cooperative action of copper and nickel catalysts and proceeds with excellent anti-Markovnikov selectivity. We demonstrate the broad scope of the reaction, which can be accomplished in the presence of esters, nitriles, aryl bromides, ethers, alkyl chlorides, anilines, and a wide range of nitrogen-containing heteroaromatic compounds. Mechanistic studies provide evidence that the copper catalyst activates the alkyne by hydrocupration, which controls both the regio- and diastereoselectivity of the overall reaction. The nickel catalyst activates the alkyl iodide and promotes cross coupling with the alkenyl copper intermediate.
- Hazra, Avijit,Chen, Jason,Lalic, Gojko
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supporting information
p. 12464 - 12469
(2019/08/20)
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- Ni-catalyzed cross-electrophile coupling between vinyl/aryl and alkyl sulfonates: Synthesis of cycloalkenes and modification of peptides
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We report here the coupling reactions between vinyl/aryl and alkyl C-O electrophiles that can be derived from chemical feedstocks and naturally occurring functional groups. This method provides an efficient approach to the synthesis of a wide range of fun
- Duan, Jicheng,Du, Yun-Fei,Pang, Xiaobo,Shu, Xing-Zhong
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p. 8706 - 8712
(2019/10/01)
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- Transition-Metal-Free Borylation of Alkyl Iodides via a Radical Mechanism
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We describe an operationally simple transition-metal-free borylation of alkyl iodides. This method uses commercially available diboron reagents as the boron source and exhibits excellent functional group compatibility. Furthermore, a diverse range of prim
- Liu, Qianyi,Hong, Junting,Sun, Beiqi,Bai, Guangcan,Li, Feng,Liu, Guoquan,Yang, Yang,Mo, Fanyang
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supporting information
(2019/07/08)
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- PHOSPHONIUM COMPOUND AND PRODUCTION METHOD THEREFOR
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The present invention provides a phosphonium compound of formula (II). Also provided is a method for producing a quaternary phosphonium compound labeled with a positron emitting radionuclide, the method comprising the step of reacting an electrophile of f
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- Selective C(sp3)?H and C(sp2)?H Fluorination of Alcohols Using Practical Auxiliaries
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Selective introduction of fluorine into molecules by the cleavage of inert C?H bonds is of central academic and synthetic interest, yet remains challenging. Given the central role of alcohols in organic chemistry as the most ubiquitous building blocks, a
- Mao, Yang-Jie,Lou, Shao-Jie,Hao, Hong-Yan,Xu, Dan-Qian
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supporting information
p. 14085 - 14089
(2018/10/15)
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- Nickel(0)-catalyzed linear-selective hydroarylation of unactivated alkenes and styrenes with aryl boronic acids
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Herein, we describe the first linear-selective hydroarylation reaction of unactivated alkenes and styrenes with aryl boronic acids, which was achieved by introducing a directing group on the alkenes. This efficient, scalable reaction serves as a method for modular assembly of structurally diverse alkyl arenes, including γ-aryl butyric acid derivatives, which are widely utilized as chemical building blocks for the synthesis of various drugs and other biologically active compounds.
- Lv, Honggui,Xiao, Li-Jun,Zhao, Dongbing,Zhou, Qi-Lin
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p. 6839 - 6843
(2018/09/11)
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- Nickel-Catalyzed C-Alkylation of Nitroalkanes with Unactivated Alkyl Iodides
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Enabled by nickel catalysis, a mild and general catalytic method for C-alkylation of nitroalkanes with unactivated alkyl iodides is described. Compatible with primary, secondary, and tertiary alkyl iodides; and tolerant of a wide range of functional groups, this method allows rapid access to diverse nitroalkanes.
- Rezazadeh, Sina,Devannah, Vijayarajan,Watson, Donald A.
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supporting information
p. 8110 - 8113
(2017/06/28)
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- Visible-Light-Promoted Remote C-H Functionalization of o-Diazoniaphenyl Alkyl Sulfones
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Visible-light irradiation of ortho-diazoniaphenyl alkyl sulfones in the presence of Ru(bpy)32+ results in remote Csp3-H functionalization. Key mechanistic steps in these processes involve intramolecular hydrogen atom transfer from Csp3-H bonds to aryl radicals to generate alkyl/benzyl radicals. Subsequent polar crossover occurs by single-electron oxidation of the alkyl/benzyl radicals to carbenium ions that then intercept nucleophiles. We have developed remote hydroxylations, etherifications, an amidation, and C-C bond formation processes using this strategy.
- Du, Shaofu,Kimball, Elizabeth Ann,Ragains, Justin R.
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supporting information
p. 5553 - 5556
(2017/10/25)
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- Stereospecific Electrophilic Fluorination of Alkylcarbastannatrane Reagents
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We report the use of isolable primary and secondary alkylcarbastannatrane nucleophiles in site-specific fluorination reactions. These reactions occur without the need for transition metal catalysis or in situ activation of the nucleophile. In the absence of the carbastannatrane backbone, alkyltin nucleophiles exhibit no activity towards fluorination. When enantioenriched alkylcarbastannatranes are employed, fluorination occurs predominately via a stereoinvertive mechanism to generate highly enantioenriched alkyl fluoride compounds. These conditions can also be extended to stereospecific chlorination, bromination, and iodination reactions.
- Ma, Xinghua,Diane, Mohamed,Ralph, Glenn,Chen, Christine,Biscoe, Mark R.
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supporting information
p. 12663 - 12667
(2017/09/11)
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- Palladium-catalyzed C-H alkylation of 2-phenylpyridines with alkyl iodides
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Palladium-catalyzed C-H alkylation reaction of 2-phenylpyridines with alkyl iodides has been successfully developed. The palladacycles obtained from 2-phenylpyridines should act as the key intermediates in the alkylation reaction.
- Wang, Xiaoling,Ji, Xiaoming,Shao, Changdong,Zhang, Yu,Zhang, Yanghui
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supporting information
p. 5616 - 5624
(2017/07/12)
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- One-Pot Transformation of Aliphatic Carboxylic Acids into N-Alkylsuccin-imides with NIS and NCS/NaI
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Primary aliphatic carboxylic acids were treated with N-iodosuccinimide (NIS) in 1,2-dichloroethane to form the corresponding alkyl iodides under warming conditions. Based on these results, those aliphatic carboxylic acids were treated with NIS, followed by the reaction with K2CO3to give the corresponding N-alkylsuccinimides in good yields in one pot. Moreover, those aliphatic carboxylic acids were treated with N-chlorosuccinimide (NCS) and NaI, followed by the reaction with K2CO3to provide the corresponding N-alkylsuccinimides in good to moderate yields in one pot. By using the present method, successive treatment of primary aliphatic carboxylic acids (10 mmol) with NIS, K2CO3, and then hydrazine provided the corresponding decarboxylated primary amines in good yield.
- Nakai, Yuhta,Moriyama, Katsuhiko,Togo, Hideo
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p. 768 - 772
(2017/01/18)
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- Use of Trifluoromethyl Groups for Catalytic Benzylation and Alkylation with Subsequent Hydrodefluorination
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The electrophilic organofluorophosphonium catalyst [(C6F5)3PF][B(C6F5)4] is shown to effect benzylation or alkylation by aryl and alkyl CF3 groups with subsequent hydrodefluorination, thus resulting in a net transformation of CF3 into CH2-aryl fragments. In the case of alkyl CF3 groups, Friedel-Crafts alkylation by the difluorocarbocation proceeded without cation rearrangement, in contrast to the corresponding reactions of alkyl monofluorides.
- Zhu, Jiangtao,Prez, Manuel,Caputo, Christopher B.,Stephan, Douglas W.
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supporting information
p. 1417 - 1421
(2016/02/14)
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- Catalytic Iodination of the Aliphatic C-F Bond by YbI3(THF)3: Mechanistic Insight and Synthetic Utility
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A facile iodination protocol of unactivated alkyl fluorides using catalytic amounts of YbI3(THF)3 in the presence of iodotrimethylsilane as a stoichiometric fluoride trapping agent is presented. 1H NMR spectroscopy demonstrates a two-step catalytic cycle where TMSI regenerates active YbI3(THF)3. Finally, the catalytic reaction is extended into a one-pot procedure to demonstrate a potential application of the method. Overall, the findings present a distinct strategy for C-F bond transformations in the presence of catalytic YbI3(THF)3.
- Janjetovic, Mario,Ekebergh, Andreas,Tr?ff, Annika M.,Hilmersson, G?ran
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supporting information
p. 2804 - 2807
(2016/07/06)
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- Mechanistic insights into Br?nsted acid-induced nucleophilic substitution of aliphatic imidazole carbamate with halide ions
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Herein we report interesting reactivity of imidazole carbamate towards nucleophilic substitution with halide ions under Br?nsted acidic conditions. Depending upon reaction conditions, halide ions could readily attack the carboxyl position and trigger decarboxylative alkyl halide formation. Alternatively, halide ions were also found to competitively undergo nucleophilic acyl substitution, which ultimately results in the generation of carbonate dimerization product.
- Saputra, Mirza A.,Forgey, Rashel L.,Henry, Jeffrey L.,Kartika, Rendy
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p. 1392 - 1396
(2015/03/04)
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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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- Light-mediated deoxygenation of alcohols with a dimeric gold catalyst
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A new protocol for the reductive deoxygenation of primary alcohols was explored. This photo-mediated method combines a novel approach to bromination of alcohols merged with the powerful reducing capability of [Au2(dppm)2]Cl2 [dppm = 1,1-bis(diphenylphosphino)methane] as a photoredox catalyst. The highly efficient methods discussed are marked by the use of UVA light-emitting diodes, which have significantly reduced reaction times and lowered setup cost.
- McCallum, Terry,Slavko, Ekaterina,Morin, Mathieu,Barriault, Louis
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supporting information
p. 81 - 85
(2015/02/18)
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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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- A straightforward synthesis of alkyl 1H-tetrazol-5-yl thioethers via a one-pot reaction of aldehydes and 1H-tetrazole-5-thiols mediated by N-tosylhydrazones
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A straightforward approach for the synthesis of alkyl 1H-tetrazol-5-yl thioethers from aldehydes and 1H-tetrazole-5-thiol through a one-pot procedure is presented. The aldehydes were first condensed with N-tosylhydrazine to generate the N-tosylhydrazones,
- Li, Le-Le,Gao, Lian-Xun,Han, Fu-She
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p. 29996 - 30000
(2015/05/13)
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- Indium(III)-catalyzed reductive monoalkylation of electron-rich benzenes with aliphatic carboxylic acids leading to arylalkane derivatives
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Described herein is the reaction of electron-rich aromatic compounds with aliphatic carboxylic acids treated with a catalytic amount (5 mol-%) of InI3, 1,1,3,3-tetramethyldisiloxane (TMDS), and molecular iodine. The reductive monoalkylation occurs smoothly to produce the corresponding arylalkane derivatives.
- Moriya, Toshimitsu,Takayama, Kentaro,Konakahara, Takeo,Ogiwara, Yohei,Sakai, Norio
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supporting information
p. 2277 - 2281
(2015/03/31)
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- Ligand-Enabled Meta-C-H Alkylation and Arylation Using a Modified Norbornene
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2-Carbomethoxynorbornene is identified as a more effective transient mediator to promote a Pd(II)-catalyzed meta-C(sp2)-H alkylation of amides with various alkyl iodides as well as arylation with previously incompatible aryl iodides. The use of a tailor-made quinoline ligand is also crucial for this reaction to proceed.
- Shen, Peng-Xiang,Wang, Xiao-Chen,Wang, Peng,Zhu, Ru-Yi,Yu, Jin-Quan
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supporting information
p. 11574 - 11577
(2015/09/28)
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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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- The effect of various zinc binding groups on inhibition of histone deacetylases 1-11
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Histone deacetylases (HDACs) have the ability to cleave the acetyl groups of ε-N-acetylated lysine residues in a variety of proteins. Given that human cells contain thousands of different acetylated lysine residues, HDACS may regulate a wide variety of processes including some implicated in conditions such as cancer and neurodegenerative disorders. Herein we report the synthesis and ina vitro biochemical profiling of a series of compounds, including known inhibitors as well as novel chemotypes, that incorporate putative new zinc binding domains. By evaluating the compound collection against all 11 recombinant human HDACs, we found that the trifluoromethyl ketone functionality provides potent inhibition of all four subclasses of the Zn2+- dependent HDACs. Potent inhibition was observed with two different scaffolds, demonstrating the efficiency of the trifluoromethyl ketone moiety as a zinc binding motif. Interestingly, we also identified silanediol as a zinc binding group with potential for future development of non-hydroxamate classa I and classa IIb HDAC inhibitors.
- Madsen, Andreas S.,Kristensen, Helle M. E.,Lanz, Gyrithe,Olsen, Christian A.
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p. 614 - 626
(2014/03/21)
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- Sterically controlled alkylation of arenes through iridium-catalyzed C-H borylation
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Complementary chemistry: A one-pot method for the site-selective alkylation of arenes controlled by steric effects is reported. The process occurs through Ir-catalyzed C-H borylation, followed by Pd- or Ni-catalyzed coupling with alkyl electrophiles. This selectivity complements that of the typical Friedel-Crafts alkylation; meta-selective alkylation of a broad range of arenes with various electronic properties and functional groups occurs in good yield with high site selectivity. Copyright
- Robbins, Daniel W.,Hartwig, John F.
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supporting information
p. 933 - 937
(2013/02/25)
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- Indium(III)-catalyzed reductive bromination and iodination of carboxylic acids to alkyl bromides and iodides: Scope, mechanism, and one-pot transformation to alkyl halides and amine derivatives
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Highly effective indium(III)-catalyzed reductive bromination or iodination of a variety of carboxylic acids with 1,1,3,3-tetramethyldisiloxane (TMDS) and a source of bromine or iodine is described. This functional group interconversion has high tolerance for several functional groups, such as halogens, a hydroxy group, a nitro group, an olefin part, and a sulfide moiety. This indium catalytic system is also applicable to the reductive iodination of aldehyded, acyl chlorides, and esters. Furthermore, this reducing system can be applied to the one-pot synthesis of alkyl halides and amine derivatives via the addition of nucleophiles. Insight into the reaction mechanism was gained via the time course of 1H and 13C NMR monitoring experiments and the corresponding stepwise reactions.
- Moriya, Toshimitsu,Yoneda, Shinichiro,Kawana, Keita,Ikeda, Reiko,Konakahara, Takeo,Sakai, Norio
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p. 10642 - 10650
(2013/11/19)
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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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- Selective C-F bond activation: Substitution of unactivated alkyl fluorides using YbI3
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F makes the break: The carbon-fluorine single bond is quite strong, thus making aliphatic C-F bond scission unusually challenging. A new methodology utilizing YbI3 leads to the conversion of a C-F bond into a C-I bond, and is compatible with various functional groups. The reaction is exceptionally selective towards alkyl fluorides and proceeds under mild conditions. Copyright
- Traeff, Annika M.,Janjetovic, Mario,Ta, Linda,Hilmersson, Goeran
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supporting information
p. 12073 - 12076
(2013/12/04)
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- Ni-catalyzed cascade cyclization-kumada alkyl-alkyl cross-coupling
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Suggesting novel disconnections: A powerful Ni-catalyzed cascade reaction involving cyclization followed by cross-coupling allows the formation of up to three alkyl-alkyl bonds in a single operation by using alkene-containing alkyl iodides and Grignard reagents (see scheme; acac=acetylacetonate; TMEDA=N,N′,N′-tetramethyl ethylenediamine). Mechanistic experimental and computational studies suggest a NiI-NiII-Ni III catalytic cycle and the intermediacy of radicals. Copyright
- Guisan-Ceinos, Manuel,Soler-Yanes, Rita,Collado-Sanz, Daniel,Phapale, Vilas B.,Bunuel, Elena,Cardenas, Diego J.
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supporting information
p. 8405 - 8410
(2013/07/25)
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- A facile and green protocol for nucleophilic substitution reactions of sulfonate esters by recyclable ionic liquids [bmim][X]
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Ionic liquids [bmim][X] (X = Cl, Br, I, OAc, SCN) are highly efficient reagents for nucleophilic substitution reactions of sulfonate esters derived from primary and secondary alcohols. The counter anions (X-) of the ionic liquids, [bmim][X], effectively replace the sufonates affording the corresponding substitution products such as alkyl halides, acetates, and thiocyanides in excellent yields. The newly developed protocol is very environmentally attractive because the reactions use stoichiometric amounts of ionic liquids as sole reagents in most cases and do not require additional solvents, any other activating reagents, non-conventional equipment, or special precautions. Moreover, these ionic liquids can be readily recycled without loss of reactivity, making the whole process greener.
- Liu, Yajun,Xu, Yongnan,Jung, Sun Ho,Chae, Junghyun
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p. 2692 - 2698,7
(2012/12/12)
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- A facile and green protocol for nucleophilic substitution reactions of sulfonate esters by recyclable ionic liquids [bmim][X]
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Ionic liquids [bmim][X] (X = Cl, Br, I, OAc, SCN) are highly efficient reagents for nucleophilic substitution reactions of sulfonate esters derived from primary and secondary alcohols. The counter anions (X-) of the ionic liquids, [bmim][X], effectively replace the sufonates affording the corresponding substitution products such as alkyl halides, acetates, and thiocyanides in excellent yields. The newly developed protocol is very environmentally attractive because the reactions use stoichiometric amounts of ionic liquids as sole reagents in most cases and do not require additional solvents, any other activating reagents, non-conventional equipment, or special precautions. Moreover, these ionic liquids can be readily recycled without loss of reactivity, making the whole process greener. Georg Thieme Verlag KG Stuttgart · New York.
- Liu, Yajun,Xu, Yongnan,Jung, Sun Ho,Chae, Junghyun
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p. 2692 - 2698
(2013/01/15)
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- Unexpected conversion of alkyl azides to alkyl iodides and of aryl azides to N-tert-butyl anilines
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In the presence of tert-butyl iodide, alkyl azides are converted into the corresponding iodides at room temperature, whereas, N-t-Bu anilines are obtained from aryl azides under the same experimental conditions. A mechanism is proposed to explain this unusual reactivity.
- Maury, Julien,Feray, Laurence,Bertrand, Michele P.,Kapat, Ajoy,Renaud, Philippe
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p. 9606 - 9611,6
(2020/08/20)
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- PROCESS FOR THE PREPARATION OF IODIDES
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This invention is directed to a process for the preparation of high yield alkyl or aryl iodide from its corresponding carboxylic acid using N-iodo amides.
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Page/Page column 29
(2012/01/05)
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- Amide-directed catalytic asymmetric hydroboration of trisubstituted alkenes
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(Chemical Equation Presented) Rhodium-catalyzed hydroborations of trisubstituted alkenes are generally slow and often suffer from competing alkene isomerization. In contrast, the trisubstituted alkene moieties contained within the framework of a β,γ-unsat
- Smith, Sean M.,Takacs, James M.
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supporting information; experimental part
p. 1740 - 1741
(2010/04/25)
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- Novel preparation of ion-supported triphenylphosphines and their synthetic utility
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Novel ion-supported Ph3P compounds, 4-(diphenylphosphino)- benzyltrimethylammonium bromide (A) and N-methyl-N-[4-(diphenylphosphino) -benzyl]pyrrolidinium bromide (B), were prepared. Because of their stability in air, ion-supported Ph3P A and B could be used for the halogenation of alcohols, the esterification of carboxylic acid with the Mitsunobu reaction, the Mizoroki-Heck reaction, and the Sonogashira reaction. The advantages of using these ion-supported Ph3P A and B are the simple isolation of the products by ether extraction due to their poor solubility in ether, and the easy recovery of the co-product, ion-supported Ph3PO, by filtration in high yields (>90%), which could be regenerated and reused for the same reactions, in the halogenation of alcohols and the esterification of carboxylic acid with the Mitsunobu reaction. On the other hand, ionic liquid reaction media containing Pd(OAc)2 or PdCl2 and ion-supported Ph3P A or B as catalysts could be reused for the same Mizoroki-Heck reaction and the Sonogashira reaction maintaining high yields, using iodotoluene with methyl acrylate and phenylacetylene, respectively.
- Imura, Yumi,Shimojuh, Naoya,Kawano, Yuhta,Togo, Hideo
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scheme or table
p. 3421 - 3426
(2010/06/19)
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- MONOACYLGLYCEROL LIPASE INHIBITORS FOR MODULATION OF CANNABINOID ACTIVITY
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Disclosed are compounds and compositions that inhibit the action of monoacylglycerol lipase (MGL) and fatty acid amide hydrolase (FAAH), methods of inhibiting MGL and FAAH, methods of modulating cannabinoid receptors, and methods of treating various disorders related to the modulation of cannabinoid receptors.
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Page/Page column 65
(2009/05/28)
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