- A general method for one-step synthesis of monofluoroiodane(III) reagents using silver difluoride
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Herein we report a new general method for one-step synthesis of four kinds of fluoroiodane(III) reagents by treating the corresponding aryl iodides with silver difluoride (AgF2). This is the first method applicable for the synthesis of all four fluoroiodane(III) reagents including p-iodotoluene difluoride (1), fluoro-benziodoxole (2), fluoro-benziodoxolone (3), and fluoro-N-acetylbenziodazole (4). AgF2 was firstly employed in the direct oxidative fluorination of iodobenzene and thus has shown its outstanding oxidation and fluorine-transfer ability. The use of AgF2 has improved the synthesis of fluoroiodane(III) reagents by shortening the reaction steps, avoiding the use of hazardous reagents, and simplifying the experimental operations. It was worth noting that we have developed the first one-step direct synthetic method for 3, while 3 can only be synthesized through Cl→F ligand exchange reaction previously.
- Du, Feng-Huan,Jia, Meng-Cheng,Ren, Jing,Zhang, Chi
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supporting information
(2022/02/16)
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- Optimization of a Benzoylpiperidine Class Identifies a Highly Potent and Selective Reversible Monoacylglycerol Lipase (MAGL) Inhibitor
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Monoacylglycerol lipase (MAGL) is the enzyme degrading the endocannabinoid 2-arachidonoylglycerol, and it is involved in several physiological and pathological processes. The therapeutic potential of MAGL is linked to several diseases, including cancer. The development of MAGL inhibitors has been greatly limited by the side effects associated with the prolonged MAGL inactivation. Importantly, it could be preferable to use reversible MAGL inhibitors in vivo, but nowadays only few reversible compounds have been developed. In the present study, structural optimization of a previously developed class of MAGL inhibitors led to the identification of compound 23, which proved to be a very potent reversible MAGL inhibitor (IC50 = 80 nM), selective for MAGL over the other main components of the endocannabinoid system, endowed of a promising antiproliferative activity in a series of cancer cell lines and able to block MAGL both in cell-based as well as in vivo assays.
- Granchi, Carlotta,Lapillo, Margherita,Glasmacher, Sandra,Bononi, Giulia,Licari, Cristina,Poli, Giulio,El Boustani, Maguie,Caligiuri, Isabella,Rizzolio, Flavio,Gertsch, Jürg,Macchia, Marco,Minutolo, Filippo,Tuccinardi, Tiziano,Chicca, Andrea
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p. 1932 - 1958
(2019/02/26)
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- 2-Iodo-N-isopropyl-5-methoxybenzamide as a highly reactive and environmentally benign catalyst for alcohol oxidation
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Several N-isopropyliodobenzamides were evaluated as catalysts for the oxidation of benzhydrol to benzophenone in the presence of Oxone (2KHSO5·KHSO4·K2SO4) as a co-oxidant at room temperature. A study on the substituent effect of the benzene ring of N-isopropyl-2-iodobenzamide on the oxidation revealed that its reactivity increased in the following order of substitution: 5-NO2 2Me, 3-OMe 5-OAc 5-Cl H, 4-OMe 5-Me 5-OMe. The oxidation of various benzylic and aliphatic alcohols using a catalytic amount of the most reactive 5-methoxy derivative successfully resulted in moderate to excellent yields of the corresponding carbonyl compounds. The high reactivity of the 5-methoxy derivative at room temperature is a result of the rapid generation of the pentavalent species from the trivalent species during the reaction. 5-Methoxy-2-iodobenzamide would be an efficient and environmentally benign catalyst for the oxidation of alcohols, especially benzylic alcohols.
- Yakura, Takayuki,Fujiwara, Tomoya,Yamada, Akihiro,Nambu, Hisanori
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supporting information
p. 971 - 978
(2019/11/11)
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- Synthesis and SAR of 4-methyl-5-pentylbenzene-1,3-diol (MPBD), produced by Dictyostelium discoideum
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4-Methyl-5-pentylbenzene-1,3-diol (MPBD) is a secondary metabolite of SteelyA polyketide synthase, which controls cell aggregation and spore maturation of Dictyostelium discoideum. In this study, chemical synthesis of MPBD and its derivatives was achieved. Structure-activity relationship (SAR) studies for antimicrobial activities against Escherichia coli and Bacillus subtilis were also conducted.
- Murata, Chihiro,Ogura, Tetsuhiro,Narita, Shuhei,Kondo, Anna P.,Iwasaki, Natsumi,Saito, Tamao,Usuki, Toyonobu
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p. 1428 - 1433
(2016/02/19)
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- A Divergent Approach to the Diastereoselective Synthesis of 3,3-Disubstituted Oxindoles from Atropisomeric N-Aryl Oxindole Derivatives
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3,3-Disubstituted oxindoles were divergently synthesized by diastereoselective transformations including nucleophilic addition, alkylation, and cycloaddition using common, axially chiral N-aryl oxindoles. Notably, high diastereoselectivities (up to >95:5) were observed with ortho-monosubstituted N-aryl oxindoles to give various oxindole scaffolds, and facile removal of the p-(benzyloxy)aryl moiety in axially twisted amides was achieved by a mild, two-step sequence.
- Nakazaki, Atsuo,Mori, Ayako,Kobayashi, Susumu,Nishikawa, Toshio
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supporting information
p. 3267 - 3274
(2016/11/29)
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- Direct carbocyclizations of benzoic acids: Catalyst-controlled synthesis of cyclic ketones and the development of tandem aHH (acyl Heck-Heck) reactions
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The formation of exo-methylene indanones and indenones from simple ortho-allyl benzoic acid derivatives has been developed. Selective formation of the indanone or indenone products in these reactions is controlled by choice of ancillary ligand. This new process has a low environmental footprint as the products are formed in high yields using low catalyst loadings, while the only stoichiometric chemical waste generated from the reactants in the transformation is acetic acid. The conversion of the active cyclization catalyst into the Hermman-Beller palladacycle was exploited in a one-pot tandem acyl Heck-Heck (aHH) reaction, and utilized in the synthesis of donepezil. Carboxylic acids in aHH: Simple ortho-allyl benzoic acid derivatives have been utilized in an acyl Heck (aH) reaction to selectively form indanones and indenones. The conversion of the active cyclization catalyst into the Hermman-Beller palladacycle was exploited in a one-pot tandem acyl Heck-Heck (aHH) reaction to form two sp 2-sp2 bonds of (E)-trisubstituted olefins.
- Miles, Kelsey C.,Le, Chi,Stambuli, James P.
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p. 11336 - 11339
(2014/10/16)
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- Design, synthesis, and biological evaluation of novel transrepression- selective liver X receptor (LXR) ligands with 5,11-dihydro-5-methyl-11- methylene-6 H-dibenz[ b, e ]azepin-6-one skeleton
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To obtain novel transrepression-selective liver X receptor (LXR) ligands, we adopted a strategy of reducing the transactivational agonistic activity of the 5,11-dihydro-5-methyl-11-methylene-6H-dibenz[b,e]azepin-6-one derivative 10, which exhibits LXR-mediated transrepressional and transactivational activity. Structural modification of 10 based on the reported X-ray crystal structure of the LXR ligand-binding domain led to a series of compounds, of which almost all exhibited transrepressional activity at 1 or 10 μM but showed no transactivational activity even at 30 μM. Among the compounds obtained, 18 and 22 were confirmed to have LXR-dependent transrepressional activity by using peritoneal macrophages from wild-type and LXR-null mice. A newly developed fluorescence polarization assay indicated that they bind directly to LXRα. Next, further structural modification was performed with the guidance of docking simulations with LXRα, focusing on enhancing the binding of the ligands with LXRα through the introduction of substituents or heteroatom(s). Among the compounds synthesized, compound 48, bearing a hydroxyl group, showed potent, selective, and dose-dependent transrepressional activity.
- Aoyama, Atsushi,Endo-Umeda, Kaori,Kishida, Kenji,Ohgane, Kenji,Noguchi-Yachide, Tomomi,Aoyama, Hiroshi,Ishikawa, Minoru,Miyachi, Hiroyuki,Makishima, Makoto,Hashimoto, Yuichi
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p. 7360 - 7377
(2012/11/07)
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- A facile synthesis of dibenzopyrroloazepinones as tetracyclic allocolchicinoids - An unusual 1,2-phenyl shift
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A facile synthesis of dibenzopyrroloazepinones via an electrophilic cyclisation of a biphenyl-acyliminium ion is described; an unusual 1,2-phenyl shift occurs when the C-1′ carbon is the more nucleophilic than the C-2′ carbon.
- Wu, Liang,Aliev, Abil E.,Caddick, Stephen,Fitzmaurice, Richard J.,Tocher, Derek A.,King, Frank D.
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supporting information; experimental part
p. 318 - 320
(2010/05/01)
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- 2-iodoxybenzenesulfonic acid as an extremely active catalyst for the selective oxidation of alcohols to aldehydes, ketones, carboxylic acids, and enones with oxone
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Electron-donating group-substituted 2-iodoxybenzoic acids (IBXs) such as5-Me-IBX (1g), 5-MeO-IBX (1h), and 4,5-Me2-IBX were superior to IBX 1a as catalysts for the oxidation of alcohols with Oxone (a trad emark of DuPont) under nonaqueous conditions, although Oxone was almost insoluble in most organic solvents. The catalytic oxidation proceeded more rapidly and cleanly in nitromethane. Furthermore, 2-iodoxybenzenesulfonic acid (IBS, 6a) was much more active than modified IBXs. Thus, we established a highly efficient and selective method for the oxidation of primary and secondary alcohols to carbonyl compounds such as aldehydes, carboxylic acids, and ketones with Oxone in nonaqueous nitromethane, acetonitrile, or ethyl acetate in the presence of 0.05-5molpercentof 6a, which was generated in situ from 2-iodobenzenesulfonic acid (7a) or its sodium salt. Cycloalkanones could be further oxidized to α,β- cycloalkenones or lactones by controlling the amounts of Oxone under the same conditions as above. When Oxone was used under nonaqueous conditions, Oxone wastes could be removed by simple filtration. Based on theoretical calculations, we considered that the relatively ionic character of the intramolecular hypervalent iodine-OSO2 bond of IBS might lower the twisting barrier of the alkoxyperiodinane intermediate 16.
- Uyanik, Muhammet,Akakura, Matsujiro,Ishihara, Kazuaki
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supporting information; experimental part
p. 251 - 262
(2009/06/28)
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