3123-97-5Relevant articles and documents
Ultrasonic effects on electroorganic processes. Part 22. Cathodic crossed hydrocoupling of acetone with acrylonitrile
Atobe, Mahito,Fujiwara, Sou,Nonaka, Tsutomu
, p. 123 - 126 (2002)
The ultrasonic effects on the cathodic-crossed hydrocoupling of acetone with acrylonitrile were examined. The total current efficiency of all products in the cathodic reduction of a mixture of acetone and acrylonitrile was little influenced by ultrasonic
Sunlight-induced C–C bond formation reaction: Radical addition of alcohols/ethers/acetals to olefins
Hayakawa, Mamiko,Shirota, Hisashi,Hirayama, Souta,Yamada, Ryuusei,Aoyama, Tadashi,Ouchi, Akihiko
, (2021)
A sunlight-induced C–C bond formation reactions upon the addition of alcohols/ethers/acetals to olefins proceeded efficiently using di-tert-butyl peroxide (DTBP). The reactions proceeded faster than many of the previously reported sunlight and many conventional lamp photolyses, typically in 3–4 h under irradiation with sunlight, in excellent yield using olefins bearing two electron withdrawing groups (EWGs) (product yield > 95 %) and in good to fair yield with olefins bearing one EWG. The yields observed for some products were ～20 % higher than those obtained using a conventional Xe lamp as the light source, which was confirmed to be due to a light intensity effect. Gram-scale experiments showed similar yields to those observed in their corresponding small-scale experiments.
Hydrocarboxylation of isoprene catalyzed by iodo-carbonylrhodium derivatives. Spectroscopic evidence for participation of H+...Rh(CO)2I2- tight ion pairs and cis-Rh(CO)2(H2O)I in catalysis
Garlaschelli, Luigi,Marchionna, Mario,Iapalucci, Maria Carmela,Longoni, Giuliano
, p. 457 - 468 (1989)
Hydrocarboxylation of isoprene catalyzed by iodocarbonylrhodium derivatives is described.Either 4-methyl-3-pentenoic (pyroterebic) acid or its lactone derivative (γ,γ-dimethyl-γ-butyrolactone) can be selectively produced in high yield depending on the experimental conditions.Spectroscopic evidence indicates the possibe partcipation of H+...Rh(CO)2I- tight ion pairs and/or cisRh(CO)2(H2O)I in the catalysis.The identification of these two new species is based on spectroscopic investigation of the interconversion reactions between solvent-separated +- ions and 2 (X=Cl, I).
Photochemical C-C bond formation between alcohols and olefins by an environmentally benign radical reaction
Ouchi, Akihiko,Liu, Chuanxiang,Kaneda, Masayuki,Hyugano, Takeshi
, p. 3807 - 3816 (2013)
A radical C-C bond formation between olefins and alcohols proceeded efficiently by simple light irradiation at room temperature. The reaction proceeded in the presence of commercially available tBuOOtBu without using the harmful elements and/or compounds that have an unpleasant smell that are often used in conventional radical reactions. In addition, the reaction did not require photosensitizers or photocatalysts, which eliminated the time-consuming separation of sensitizers after the reaction, or the synthesis of photocatalysts as reported in previous procedures. A radical C-C bond formation between olefins and alcohols proceeded efficiently by simple light irradiation at room temperature without using the harmful elements often used in conventional radical reactions. Copyright
N-Ammonium Ylide Mediators for Electrochemical C-H Oxidation
Saito, Masato,Kawamata, Yu,Meanwell, Michael,Navratil, Rafael,Chiodi, Debora,Carlson, Ethan,Hu, Pengfei,Chen, Longrui,Udyavara, Sagar,Kingston, Cian,Tanwar, Mayank,Tyagi, Sameer,McKillican, Bruce P.,Gichinga, Moses G.,Schmidt, Michael A.,Eastgate, Martin D.,Lamberto, Massimiliano,He, Chi,Tang, Tianhua,Malapit, Christian A.,Sigman, Matthew S.,Minteer, Shelley D.,Neurock, Matthew,Baran, Phil S.
supporting information, p. 7859 - 7867 (2021/05/26)
The site-specific oxidation of strong C(sp3)-H bonds is of uncontested utility in organic synthesis. From simplifying access to metabolites and late-stage diversification of lead compounds to truncating retrosynthetic plans, there is a growing need for new reagents and methods for achieving such a transformation in both academic and industrial circles. One main drawback of current chemical reagents is the lack of diversity with regard to structure and reactivity that prevents a combinatorial approach for rapid screening to be employed. In that regard, directed evolution still holds the greatest promise for achieving complex C-H oxidations in a variety of complex settings. Herein we present a rationally designed platform that provides a step toward this challenge using N-ammonium ylides as electrochemically driven oxidants for site-specific, chemoselective C(sp3)-H oxidation. By taking a first-principles approach guided by computation, these new mediators were identified and rapidly expanded into a library using ubiquitous building blocks and trivial synthesis techniques. The ylide-based approach to C-H oxidation exhibits tunable selectivity that is often exclusive to this class of oxidants and can be applied to real-world problems in the agricultural and pharmaceutical sectors.
ZnI2/Zn(OTf)2-TsOH: A versatile combined-Acid system for catalytic intramolecular hydrofunctionalization and polyene cyclization
Chou, Ting-Hung,Yu, Bo-Hung,Chein, Rong-Jie
supporting information, p. 13522 - 13525 (2019/11/14)
A mild and efficient combined-Acid system using a zinc(ii) salt [ZnI2 or Zn(OTf)2] and p-Toluene sulfonic acid (TsOH) was investigated for catalytic cationic cyclizations, including intramolecular hydrocarboxylation, hydroalkoxylation, hydroamination, hydroamidation, hydroarylation and polyene cyclizations. This reaction provides easy access to five-and six-membered O-and N-containing saturated heterocyclic compounds, tetrahydronaphthalene derivatives and polycyclic skeletons in excellent yield with perfect Markovnikov selectivity and under mild conditions. The operational simplicity, broad applicability, and use of inexpensive commercially available catalysts make this protocol superior to existing methodologies.
C-H oxygenation at tertiary carbon centers using iodine oxidant
Kiyokawa, Kensuke,Ito, Ryo,Takemoto, Kenta,Minakata, Satoshi
supporting information, p. 7609 - 7612 (2018/07/15)
An oxidation system in which iodic acid (HIO3) is used as an oxidant in the presence of N-hydroxyphthalimide (NHPI) permitted the selective hydroxylation of tertiary C-H bonds and the lactonization of carboxylic acids containing a tertiary carbon center. These reactions are operationally simple and proceed under metal-free conditions using commercially available reagents, thus offering an ideal tool for the efficient oxidation of C-H bonds at tertiary carbon centers.
Silver-Catalyzed Decarboxylative Bromination of Aliphatic Carboxylic Acids
Tan, Xinqiang,Song, Tao,Wang, Zhentao,Chen, He,Cui, Lei,Li, Chaozhong
supporting information, p. 1634 - 1637 (2017/04/11)
The silver-catalyzed Hunsdiecker bromination of aliphatic carboxylic acids is described. With Ag(Phen)2OTf as the catalyst and dibromoisocyanuric acid as the brominating agent, various aliphatic carboxylic acids underwent decarboxylative bromination to provide the corresponding alkyl bromides under mild conditions. This method not only is efficient and general but also enjoys wide functional group compatibility. An oxidative radical mechanism involving Ag(II) intermediates is proposed.
Cooperative Polar/Steric Strategy in Achieving Site-Selective Photocatalyzed C(sp3)?H Functionalization
Yamada, Keiichi,Fukuyama, Takahide,Fujii, Saki,Ravelli, Davide,Fagnoni, Maurizio,Ryu, Ilhyong
supporting information, p. 8615 - 8618 (2017/06/30)
Synergistic control over the SH2 transition states of hydrogen abstraction exploiting polar and steric effects provides a promising cooperative strategy for site-selective C(sp3)?H functionalization using decatungstate anion photocatalysis. By using this photocatalytic approach, the C?H bonds of substituted lactones and cyclic ketones were functionalized selectively. In the remarkable case of 2-isoamyl 4-tert-butyl cyclohexanone (1 t) bearing five methyl, five methylene, and three methine C?H bonds, one methine C?H bond in the isoamyl tether was selectively functionalized.
From DNA to catalysis: A thymine-acetate ligated non-heme iron(III) catalyst for oxidative activation of aliphatic C-H bonds
Al-Hunaiti, Afnan,R?is?nen, Minn?,Repo, Timo
, p. 2043 - 2046 (2016/02/05)
A non-heme, iron(iii)/THA(thymine-1-acetate) catalyst together with H2O2 as an oxidant is efficient in oxidative C-H activation of alkanes. Although having a higher preference for tertiary C-H bonds, the catalyst also oxidizes aliphatic secondary C-H bonds into carbonyl compounds with good to excellent conversions. Based on the site selectivity of the catalyst and our mechanistic studies the reaction proceeds via an Fe-oxo species without long lived carbon centered radicals.
