- Electrochemical behavior of N-oxyphthalimides: Cascades initiating self-sustaining catalytic reductive N―O bond cleavage
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N-oxyphthalimides are stable and easily accessible compounds that can produce oxygen radicals upon 1-electron reduction. We present a systematic study of electrochemical properties of N-oxyphthalimide derivatives (PI-ORs) in DMF by cyclic voltammetry. In all cases, electron transfer to the substrate leads to decomposition of the intermediate radical anion via the N―O bond cleavage. In the case of benzyloxyphthalimide or its derivatives containing electron-donating substituents, reductive electron transfer induces the chain decomposition of the substrate to phthalimide (PI) radical-anion and the corresponding carbonyl compound. The PI radical-anion product is a powerful reductant that can transfer an electron to the reactant PI-OR, thus establishing a catalytic cycle for reductive N―O scission. This self-catalytic process is reflected in a considerable decrease in the reduction current for the substrate (-/molecule). By contrast, reductive fragmentations of benzyl derivatives containing electron-withdrawing substituents in the aromatic ring or at the benzylic position, as well as tosyl and alkyl derivatives, occur via a 1-electron mechanism. A sequence of N―O and C―C scissions was engineered to support the intermediacy of O-centered radicals in these processes.
- Syroeshkin, Mikhail A.,Krylov, Igor B.,Hughes, Audrey M.,Alabugin, Igor V.,Nasybullina, Darya V.,Sharipov, Mikhail Yu.,Gultyai, Vadim P.,Terent'ev, Alexander O.
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Read Online
- PCET-Based Ligand Limits Charge Recombination with an Ir(III) Photoredox Catalyst
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Upon photoinitiated electron transfer, charge recombination limits the quantum yield of photoredox reactions for which the rates for the forward reaction and back electron transfer are competitive. Taking inspiration from a proton-coupled electron transfe
- Sayre, Hannah,Ripberger, Hunter H.,Odella, Emmanuel,Zieleniewska, Anna,Heredia, Daniel A.,Rumbles, Garry,Scholes, Gregory D.,Moore, Thomas A.,Moore, Ana L.,Knowles, Robert R.
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supporting information
p. 13034 - 13043
(2021/09/03)
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- Preparation of cyclic imides from alkene-tethered amides: Application of homogeneous Cu(ii) catalytic systems
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A Cu-based homogeneous catalytic system was proposed for the preparation of imides from alkene-tethered amides. Here, O2 acted as a terminal oxidant and a cheap and easily available oxygen source. The cleavage of CC bonds and the formation of C
- Chen, Suqing,Liu, Zhenghui,Mu, Tiancheng,Ou, Hualin,Tan, Xingxing,Wang, Peng,Yan, Zhenzhong,Yu, Dongkun,Zhao, Xinhui
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p. 7698 - 7707
(2020/03/13)
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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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- Rhodium(iii)-catalyzed directed amidation of unactivated C(sp3)-H bonds to afford 1,2-amino alcohol derivatives
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A rhodium-catalyzed directed C(sp3)-H amidation to afford 1,2-amino alcohol oxime derivatives has been developed with good yields and a broad substrate scope. In previous methods for this type of reaction, 1-arylethan-1-ol oxime analogues were
- Dong, Yi,Chen, Jiajing,Xu, Heng
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supporting information
p. 11096 - 11099
(2018/11/21)
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- Palladium-catalyzed intermolecular amination of unactivated C(sp3)-H bonds via a cleavable directing group
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Palladium-catalyzed intermolecular amination of unactivated C(sp3)-H bonds was developed. Using NFSI as both the amino source and the oxidant, this protocol operates under mild conditions with excellent terminal selectivity and a broad substrate scope. Moreover, the directing group can be easily removed to produce 1,2-amino alcohols.
- Jin, Lianwen,Zeng, Xiaoli,Li, Siyang,Hong, Xuechuan,Qiu, Guofu,Liu, Peng
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supporting information
p. 3986 - 3989
(2017/04/11)
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- High activity N - oxyl new nicotine analogs and its preparation method and application (by machine translation)
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The invention belongs to the insecticide field, and in particular relates to high activity N - oxyl anabasine analogue and its preparation method and application. The invention by introducing the flexible side chain, has offered a kind of novel structure, pesticidal activity with the pyrrole insectforest quite, to the bee safely high activity N - oxyl new nicotine analogs insecticide. The insecticide solves the drug resistance of the Imidacloprid and toxic properties of the bees, can be advantageous protection of crops, horticultural plants, fruit and vegetables and the like, to prevent the emergence of the pest, increases its output, while at the same time for the activity and beneficial biological toxicity of the insecticide development explored a new path. (by machine translation)
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Paragraph 0046-0049
(2017/07/06)
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- Synthesis of 1,2-amino alcohols via catalytic C-H amidation of sp3 methyl C-H bonds
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Herein a new synthetic route to 1,2-amino alcohols is presented by using C-H amidation of sp3 methyl C-H bonds as a key step. Readily available alcohols were employed as starting materials after converting them to removable ketoxime chelating g
- Kang, Taek,Kim, Heejeong,Kim, Jeung Gon,Chang, Sukbok
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supporting information
p. 12073 - 12075
(2014/12/11)
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- NOVEL VASCULAR LEAKAGEAGE INHIBITOR
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The present disclosure relates to a novel vascular leakage inhibitor. The novel vascular leakage inhibitor of the present invention inhibits the apoptosis of vascular endothelial cells, inhibits the formation of actin stress fibers induced by VEGF, and enhances the cortical actin ring structure, thereby inhibiting vascular leakage. Accordingly, the vascular leakage inhibitor of the present invention can prevent or treat various diseases caused by vascular leakage. Since the vascular leakage inhibitor of the present invention is synthesized from commercially available or easily synthesizable pregnenolones, it has remarkably superior feasibility of commercial synthesis.
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Paragraph 0097
(2015/01/07)
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- Catalytic functionalization of unactivated sp3 C-H bonds via exo -directing groups: Synthesis of chemically differentiated 1,2-Diols
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We describe a Pd-catalyzed site-selective functionalization of unactivated aliphatic C-H bonds, providing chemically differentiated 1,2-diols from monoalcohol derivatives. The oxime was employed as both a directing group (DG) and an alcohol surrogate for this transformation. As demonstrated in a range of substrates, the C-H bonds β to the oxime group are selectively oxidized. Besides activation of the methyl groups, methylene groups (CH2) in cyclic substrates and methine groups (CH) at bridge-head positions can also be functionalized. In addition, an intriguing oxidative skeleton rearrangement was observed using the menthol-derived substrate. The use of exo-directing groups in C-H activation, as illustrated in this work, would potentially open doors for the discovery of new transformations and new cleavable DGs.
- Ren, Zhi,Mo, Fanyang,Dong, Guangbin
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supporting information
p. 16991 - 16994,4
(2020/09/02)
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- The discovery of the benzhydroxamate MEK inhibitors CI-1040 and PD 0325901
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A novel series of benzhydroxamate esters derived from their precursor anthranilic acids have been prepared and have been identified as potent MEK inhibitors. 2-(2-Chloro-4-iodo-phenylamino)-N-cyclopropylmethoxy-3,4-difluoro-benzam ide, CI-1040, was the first MEK inhibitor to demonstrate in vivo activity in preclinical animal models and subsequently became the first MEK inhibitor to enter clinical trial. CI-1040 suffered however from poor exposure due to its poor solubility and rapid clearance, and as a result, development of the compound was terminated. Optimization of the diphenylamine core and modification of the hydroxamate side chain for cell potency, solubility, and exposure with oral delivery resulted in the discovery of the clinical candidate N-(2,3-dihydroxy-propoxy)-3,4-difluoro-2-(2-fluoro-4-iodo-phenylamino)-b enzamide PD 0325901.
- Barrett, Stephen D.,Bridges, Alexander J.,Dudley, David T.,Saltiel, Alan R.,Fergus, James H.,Flamme, Cathlin M.,Delaney, Amy M.,Kaufman, Michael,LePage, Sophie,Leopold, Wilbur R.,Przybranowski, Sally A.,Sebolt-Leopold, Judith,Van Becelaere, Keri,Doherty, Annette M.,Kennedy, Robert M.,Marston, Dan,Howard Jr., W. Allen,Smith, Yvonne,Warmus, Joseph S.,Tecle, Haile
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supporting information; experimental part
p. 6501 - 6504
(2009/10/01)
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- Synthesis and fungicidal activity of macrolactams and macrolactones with an oxime ether side chain
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Three series of novel macrolactams and macrolactones - 12-alkoxyimino- tetradecanlactam, 12-alkoxyiminopentadecanlactam, and 12-alkoxyiminodecanlactone derivatives (7A, 7B, and 7C) - were synthesized from corresponding 12-oxomacrolactams and 12-oxomacrolactone. Their structures were confirmed by 1H NMR and elemental analysis. The Z and E isomers of 7A and 7B were separated, and their configurations were determined by 1H NMR. These compounds showed fair to excellent fungicidal activities against Rhizoctonia solani Kuehn. It is interesting that the Z and E isomers of most of the compounds have quite different fungicidal activities. The fact that the compounds have a gradual increase of fungicidal activity in the order of 7A, 7C, and 7B indicated that the macrocyclic derivatives with a hydrogen-bonding acceptor (=N-O-) and a hydrogen-bonding donor (-CONH-) on the ring, and a three methylenes distance (CH2CH2CH2) between these two functional groups, exhibited the best fungicidal activity. The bioassay also showed that 7B not only has good fungicidal activity but also may have a broad spectrum of fungicidal activities.
- Huang, Jia-Xing,Jia, Yue-Mei,Liang, Xiao-Mei,Zhu, Wei-Juan,Zhang, Jian-Jun,Dong, Yan-Hong,Yuan, Hui-Zu,Qi, Shu-Hua,Wu, Jin-Ping,Chen, Fu-Heng,Wang, Dao-Quan
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experimental part
p. 10857 - 10863
(2009/11/30)
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- Control of parasites in animals by the use of novel trifluoromethanesulfonanilide oxime ether derivatives
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Novel trifluoromethanesulfonanilide oxime ether compounds useful for controlling endo and/or ectoparasites in the environment are provided, together with methods of making the same, and methods of using the inventive compounds to treat parasite infestations in vivo or ex vivo.
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Page/Page column 32; 33
(2010/10/20)
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- Synthesis and antienteroviral activity of a series of novel, oxime ether-containing pyridyl imidazolidinones
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A series of pyridyl imidazolidinones were synthesized and their antiviral activity was evaluated in a plaque reduction assay. It was found that the pyridyl imidazolidinone with an ethyl oxime ether functionality, 8b, exhibited extremely high activity against human enterovirus 71.
- Chern, Jyh-Haur,Lee, Chung-Chi,Chang, Chih-Shiang,Lee, Yen-Chun,Tai, Chia-Liang,Lin, Ying-Ting,Shia, Kak-Shan,Lee, Ching-Yin,Shih, Shin-Ru
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p. 5051 - 5056
(2007/10/03)
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- Improved synthesis of N-alkoxyphthalimides
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Synthetically useful N-alkoxyphthalimide derivatives can be conveniently prepared in high yields from the reactions of N-hydroxyphthalimide with alkyl halides by using DBU in DMF.
- Kim,Kim,Ryu
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p. 1427 - 1432
(2007/10/02)
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- Factors Affecting the Stability and Equilibria of Free Radicals. XIII. N-Alkoxy- and N-Aralkoxypicrylamines and ESR Spectra of the Corresponding Capto-Dative Persistent Aminyls
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Five O-alkylhydroxylamines and three aralkylhydroxylamines have been picrylated to give O-alkyl-N-picrylhydroxylamines.These were converted to the corresponding N-(ar)alkoxy-picryl-aminyl radicals in toluene solution, and the ESR spectra were recorded.Simulations of the spectra with reasonable parameters and g values confirm the expected radical structures.Hyperfine coupling constants for nuclei in the picryl (acceptor) ring are smaller than those for the (ar)alkoxy group.This indication of competitive electron pair delocalization to the picryl ring, together with the long lifetimes of these radicals (compared with the symmetrically substituted diphenylaminyls), both support the concept of captodative stabilization.
- Stanciuc, Gabriela,Caproiu, M. Teodor,Caragheorgheopol, Agneta,Caldararu, Horia,Balaban, Alexandru T.,Walter, Robert I.
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- Hydroxyimino and alkoxyimino derivatives of 1,4-dihydropyridine and anti-hypertensive compositions
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Compounds of formula I: STR1 are described in which R1 is a linear or branched alkyl radical containing between 1 and 5 carbon atoms, the alkyl radical being unsubstituted or substituted by an alkoxy group; R2 is an unsubstituted phenyl of phenyl substituted by a nitro group; R3 is hydrogen or a linear or branched alkyl residue containing between 1 and 4 carbon atoms, the alkyl radical being unsubstituted or substituted by at least one alkoxy or fluorine atom or both alkoxy and fluorine atoms; R4 is hydrogen or a linear or branched alkyl containing between 1 and 4 carbon atoms, the alkyl radical being unsubstituted or substituted by alkoxy, carbalkoxy, dialkylamino, 1-aryl or 1-heteroarylpiperazinyl, aryl or a monocyclic 5 or 6 membered heterocycle in which at least one of the heteroatoms is N,O,S such as 1-piperidinyl, 4-morpholinyl or R4 is alkenyl or cyclo(C3 -C6)alkyl; and enantiomers, racemates, diastereoisomers and isomers (E) and (Z) and their salts with pharmaceutically acceptable acids. The novel compounds exhibit calcium-antagonistic activity.
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