- The Versatility of the Aryne-Imine-Aryne Coupling for the -Synthesis of Acridinium Photocatalysts
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The increasing use of acridinium photocatalysts as sustainable alternative to precious metal-based counterparts encourages the design and efficient synthesis of distinct catalyst structures. Herein, we report our exploration of the scope of the aryne-imin
- Hutskalova, Valeriia,Sparr, Christof
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supporting information
(2021/07/31)
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- A Three-Phase Four-Component Coupling Reaction: Selective Synthesis of o-Chloro Benzoates by KCl, Arynes, CO2, and Chloroalkanes
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A transition-metal-free three-phase four-component coupling reaction (3P-4CR) involving KCl, arynes, chloroalkanes and CO2 has been reported for the first time, enabling the incorporation of both chloro and CO2 into an aryne simultaneously. The reactions for the synthesis of different types of o-chloro benzoates can be selectively modulated by the chloroalkane utilized. The corresponding products can be alternatively transformed for postsynthetic functionalizations conveniently.
- Jiang, Huanfeng,Zhang, Yu,Xiong, Wenfang,Cen, Jinghe,Wang, Lu,Cheng, Ruixiang,Qi, Chaorong,Wu, Wanqing
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supporting information
p. 345 - 349
(2019/01/24)
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- Trifluoromethyl aryl sulfonates (TFMS): An applicable trifluoromethoxylation reagent
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Fluorine is probably another favorite hetero-atom for incorporation into small molecules after nitrogen. Among many fluorine-containing groups, trifluoromethyl aryl ethers (ArOCF3) have unique properties in drug design and are difficult to be synthesized, and many different methods were developed to prepare them. A novel one-pot synthesis of o-iodine-aryl trifluoromethyl ethers (ArOCF3I) was described by the reaction of trifluoromethoxylation and iodination with trifluoromethyl aryl sulfonates (TFMS) in this manuscript. The reaction conditions were optimized by screening different solvents, crown ethers, substrates and the ratios and the yields of products were in moderate to high yields (up to 86%).
- Lei, Meng,Miao, Hang,Wang, Xueyuan,Zhang, Wen,Zhu, Chengjian,Lu, Xiaqiang,Shen, Jian,Qin, Yanru,Zhang, Haoyang,Sha, Sijia,Zhu, Yongqiang
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supporting information
p. 1389 - 1392
(2019/04/30)
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- Construction of Phenanthrenes and Chrysenes from β-Bromovinylarenes via Aryne Diels-Alder Reaction/Aromatization
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A highly efficient transition-metal-free general method for the synthesis of polycyclic aromatic hydrocarbons like phenanthrenes and chrysenes (and tetraphene) from β-bromovinylarenes and arynes has been developed. The reactions proceed via an aryne Diels-Alder (ADA) reaction, followed by a facile aromatization. This is the first report on direct construction of chrysenes (and tetraphene) using the ADA approach. Unlike the literature method which is limited to only 9/10-substituted derivatives, this method gives access to a wide variety of functionalized phenanthrenes.
- Singh, Vikram,Verma, Ram Subhawan,Khatana, Anil K.,Tiwari, Bhoopendra
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supporting information
p. 14161 - 14167
(2019/10/28)
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- Tandem nucleophilic addition-cycloaddition of arynes with α-iminoesters: Two concurrent pathways to imidazolidines
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The tandem nucleophilic addition-cycloaddition reaction has been developed for the synthesis of functionalized imidazolidine derivatives. A variety of α-iminoesters and aryne precursors were well tolerated under the mild reaction conditions. This asymmetric cycloaddition afforded imidazolidine derivatives with high yields, complete regioselectivities, and excellent diastereo- and enantioselectivities. Aryne-induced ylides working as 1,3-dipoles for asymmetric cycloaddition are the notable feature of the present reaction. In the tandem reaction, the [3+2] cycloaddition of aryne-induced ylides with metallized α-iminoesters and metal-catalyzed [3+2] cycloaddition of azomethine ylide with α-iminoesters are two concurrent pathways to imidazolidines.
- Jia, Hao,Guo, Zhenyan,Liu, Honglei,Mao, Biming,Shi, Xueyan,Guo, Hongchao
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supporting information
p. 7050 - 7053
(2018/07/05)
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- Synthesis of 2-arylbenzofuran-3-carbaldehydes: via an organocatalytic [3+2] annulation/oxidative aromatization reaction
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A novel organocatalytic [3+2] annulation/oxidative aromatization reaction of enals with 2-halophenols or β-naphthols is reported. This process enables chemo- and regioselective access to 2-arylbenzofuran-3-carbaldehydes without the use of transition metals or strong oxidants. Preliminary mechanistic studies reveal that an unprecedented, organocatalytic, direct α-arylation pathway is involved.
- Zhang, Huiwen,Ma, Chunmei,Zheng, Ziwei,Sun, Rengwei,Yu, Xinhong,Zhao, Jianhong
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supporting information
p. 4935 - 4938
(2018/05/23)
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- Indanol-Based Chiral Organoiodine Catalysts for Enantioselective Hydrative Dearomatization
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Rapid development in the last decade has rendered chiral organoiodine(I/III) catalysis a reliable methodology in asymmetric catalysis. However, due to the severely limited numbers of effective organoiodine catalysts, many reactions still give low to modes
- Hashimoto, Takuya,Shimazaki, Yuto,Omatsu, Yamato,Maruoka, Keiji
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supporting information
p. 7200 - 7204
(2018/06/15)
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- Practical, mild and efficient electrophilic bromination of phenols by a new I(iii)-based reagent: The PIDA-AlBr3 system
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A practical electrophilic bromination procedure for phenols and phenol-ethers was developed under efficient and very mild reaction conditions. A broad scope of arenes was investigated, including the benzimidazole and carbazole core as well as analgesics such as naproxen and paracetamol. The new I(iii)-based brominating reagent PhIOAcBr is operationally easy to prepare by mixing PIDA and AlBr3. Our DFT calculations suggest that this is likely the brominating active species, which is prepared in situ or isolated after centrifugation. Its stability at 4 °C after preparation was confirmed over a period of one month and no significant loss of its reactivity was observed. Additionally, the gram-scale bromination of 2-naphthol proceeds with excellent yields. Even for sterically hindered substrates, a moderately good reactivity is observed.
- Satkar, Yuvraj,Ramadoss, Velayudham,Nahide, Pradip D.,García-Medina, Ernesto,Juárez-Ornelas, Kevin A.,Alonso-Castro, Angel J.,Chávez-Rivera, Ruben,Jiménez-Halla, J. Oscar C.,Solorio-Alvarado, César R.
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p. 17806 - 17812
(2018/05/28)
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- Access to Air-Stable 1,3-Diphosphacyclobutane-2,4-diyls by an Arylation Reaction with Arynes
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Tuning of the physicochemical properties of the 1,3-diphosphacyclobutane-2,4-diyl unit is attractive in view of materials applications. The use of arynes is shown to be effective for installing relatively electron rich aryl substituents into the open-shell singlet P-heterocyclic system. Treatment of the sterically encumbered 1,3-diphosphacyclobuten-4-yl anion with ortho-silylated aryl triflates in the presence of fluoride under appropriate conditions afforded the corresponding 1-aryl 1,3-diphosphacyclobutane-2,4-diyls. The air-stable open-shell singlet P-heterocycles exhibit considerable electron-donating character, and the aromatic substituent influences the open-shell character, which is thought to be related to the property of p-type semiconductivity. The P-arylated 1,3-diphosphacyclobutane-2,4-diyl systems can be further utilized as detectors of hydrogen fluoride (HF), which causes a remarkable change in their photoabsorption properties.
- Ueta, Yasuhiro,Mikami, Koichi,Ito, Shigekazu
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supporting information
p. 7525 - 7529
(2016/07/06)
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- Palladium-catalyzed paraformaldehyde insertion: A three-component synthesis of benzofurans
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An efficient procedure for 2-aroylbenzofuran preparation from 2-bromophenols, phenacyl bromides and paraformaldehyde is described. The cheap and stable paraformaldehyde served as the carbon source via an in situ formylation reaction.
- Cheng, Xiufang,Peng, Yi,Wu, Jun,Deng, Guo-Jun
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supporting information
p. 2819 - 2823
(2016/03/12)
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- Experimental and Theoretical Investigations of the Bromination of Phenols with β and γ Aliphatic Substituents, including Rings
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Bromination reactions of substituted and ring fused phenols were studied by both experiment (t-BuNH-Br) and computation (density functional theory). The outcomes support each other, indicating a clear and predictable regioselective preference among 3,4-bis-alkylated and 3,4-ring-fused phenols.
- Zhang, Jinsong,Chang, Xiao,Bowman, Erich C.,Holt, Carter J.,Lodewyk, Michael W.,Miller, Randy M.,Xia, Guangming
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p. 9292 - 9296
(2015/09/28)
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- Imidazopyridine Macrocycles as Inhibitors of Human Immunodeficiency Virus Replication
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The disclosure generally relates to compounds of formula I, including compositions and methods for treating human immunodeficiency virus (HIV) infection. The disclosure provides novel inhibitors of HIV, pharmaceutical compositions containing such compound
- -
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Paragraph 0181
(2015/09/22)
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- INHIBITORS OF HUMAN IMMUNODEFICIENCY VIRUS REPLICATION
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The disclosure generally relates to compounds of formula (I), including compositions and methods for treating human immunodeficiency virus (HIV) infection. The disclosure provides novel inhibitors of HIV, pharmaceutical compositions containing such compou
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Page/Page column 163
(2014/03/22)
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- New synthesis of A-ring aromatic strigolactone analogues and their evaluation as plant hormones in pea (pisum sativum)
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A new general access to A-ring aromatic strigolactones, a new class of plant hormones, has been developed. The key transformations include in sequence ring-closing metathesis, enzymatic kinetic resolution and a radical cyclization with atom transfer to install the tricyclic ABC-ring system. The activity as plant hormones for the inhibition of shoot branching in pea of various analogues synthesized by this strategy is reported. Inhibiting shoot branching: A new general access to A-ring aromatic strigolactones (see scheme), a new class of plant hormones, has been developed. The biological activity of various analogues synthesized by this strategy for inhibiting bud outgrowth in pea was evaluated. Copyright
- Chen, Victor X.,Boyer, Fran?ois-Didier,Rameau, Catherine,Pillot, Jean-Paul,Vors, Jean-Pierre,Beau, Jean-Marie
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supporting information
p. 4849 - 4857
(2013/05/22)
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- Stereochemistry, total synthesis, and biological evaluation of the new plant hormone solanacol
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The first total synthesis of solanacol, a member of the strigolactone family, features ring-closing metathesis, enzymatic kinetic resolution, and atom-transfer radical cyclization. This defines the stereostructure of the natural product. The best hormonal
- Chen, Victor X.,Boyer, Franois-Didier,Rameau, Catherine,Retailleau, Pascal,Vors, Jean-Pierre,Beau, Jean-Marie
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scheme or table
p. 13941 - 13945
(2011/03/23)
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- Palladium-catalyzed reactions of cyclohexadienones: Regioselective cyclizations triggered by alkyne acetoxylation
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Regioselective cyclizations of alkyne-tethered cyclohexadienones can be accomplished under palladium catalysis. The cyclization involves an initial Pd-mediated acetoxylation of the alkyne, followed by migratory insertion and protonolysis of the resulting
- Tello-Aburto, Rodolfo,Harned, Andrew M.
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supporting information; experimental part
p. 3998 - 4000
(2009/12/03)
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- First synthesis of nitro-substituted 2,2-diphenyl-2H-1-benzopyrans via the ipso-nitration reaction
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The first synthesis of a series of nitro-substituted 2,2-diphenyl-2H-1-benzopyrans is reported. Our synthetic approach is based on a linear synthesis in two steps from appropriate brominated 2,2-diphenyl-2H-1-benzopyrans 12-17, which requires the preliminary preparation of bromophenols 7-11. These latter were easily obtained by the reaction of phenols 1-5 with a mild and selective brominating agent tetrabutylammonium tribromide (TBA·Br3). The key intermediates 12-17 were efficiently elaborated through an univocal classic chromenization between the commercially available 1,1-diphenyl-2-yn-1-ol and the brominated phenols 6-11. The compounds 12-17 so obtained were converted into arylboronic acids 18-23 by a metalation/boronylation sequence, followed by acid hydrolysis. From advanced building blocks 18-23, the introduction of nitro group, which constitutes the ultimate step of our strategy, was achieved by an ipso-nitration reaction using the Crivello's reagent. This highly selective method provides only the ipso-nitrated products 24-29 in moderate to high yield.
- Bougdid, Lahoussine,Heynderickx, Arnault,Delbaere, Stéphanie,Moustrou, Corinne
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p. 8242 - 8249
(2008/02/05)
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- Dissymmetric Calixarenes with C4- and C2-Symmetry. Synthesis, X-ray Structures, Conformational Fixation, and 1H NMR Spectroscopic Studies
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Six dissymmetric calixarenes with C4 symmetry consisting of four 3,4-disubstituted phenolic units have been obtained by condensation of the respective 2- or 6-hydroxymethylated phenols.The regular incorporation of the phenolic units into the
- Andreetti, Giovanni D.,Boehmer, Volker,Jordon, J. Graham,Tabatabai, Moniralsadat,Ugozzoli, Franco,et al.
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p. 4023 - 4032
(2007/10/02)
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- REACTION OF THIANTHRENE CATION RADICAL WITH DIARYLMERCURIALS. SEARCH FOR SINGLE ELECTRON TRANSFER IS ELUSIVE
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Diarylmercurials (Ar2Hg) with Ar = p-tolyl Ib, o-tolyl-Ic, p-anisyl Id and 2-allyloxy-4,5-dimethylphenyl Ie, reacted with thianthrene cation radical perchlorate (ThClO4-) in two stoichiometric ratios: 2 : 1 and 4 : 1 (Thcation
- Hoque, A. K. M. M.,Shine, Henry J.,Venkatachalam, T. Krishnan
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- Synthesis of vicinal 2,3-dialkyl-6-hydroxybenzophenones by titanium tetrachloride catalyzed Fries rearrangement of 3,4-dialkylphenyl benzoates
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The titanium(IV) chloride-mediated Fries rearrangement of 3,4-dialkylphenyl benzoates 1 yields mainly 4,5-dialkyl-2-hydroxybenzophenones 2 in high yield. We describe here a new access to the unknown vicinal 2,3-dialkyl-6-hydroxybenzophenones 3, which is b
- Martin,Demerseman
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p. 738 - 740
(2007/10/02)
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- Dissymmetric Calixarenes with C2 and C4 Symmetry
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Chiral calixarenes with C2 and C4 symmetry have been prepared and transformed into stable derivatives in the cone conformation.Their structures were established by 1H NMR and mass spectra and by an X-ray structure of a tetraester
- Wolff, Artur,Boehmer, Volker,Vogt, Walter,Ugozzoli, Franco,Andreetti, Giovanni D.
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p. 5665 - 5667
(2007/10/02)
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- Halogenation Using Quaternary Ammonium Polyhalides. IV. Selective Bromination of Phenols by Use of Tetraalkylammonium Tribromides
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Reaction of phenols with calculated amounts of benzyltrimethylammonium tribromide or tetrabutylammonium tribromide in dichloromethane-methanol for 0.5-1 h under mild conditions gave, selectively, the objective mono-, di-, or tribromophenols in good yields.
- Kajigaeshi, Shoji,Kakinami, Takaaki,Okamoto, Tsuyoshi,Nakamura, Hiroko,Fujikawa, Masahiro
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p. 4187 - 4189
(2007/10/02)
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- ipso Halogenation. II. Bromination of phenols, isomerisation and disproportionation of bromophenols, and dione-phenol rearrangement of bromodienones
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Bromination of p-cresol, bromo-p-cresol, 3,4-dimethylphenol, and mesitol in trifluoromethanesulfonic acid gices as the main product the bromo derivative with bromine meta to hydroxyl, a result attributed to the intermediate formation of a bromodienone and its rearrangement.Phenols does not give m-bromophenol in trifluoromethanesulfonic acid. 4-Bromo-2,4,6-trimethylcyclohexa-2,5-dienone rearranges to 3-bromomesitol in trifluoromethanesulfonic acid and, similarly, 2,4,6-tribromo-4-methylcyclohexa-2,5-dienone rearranges to 3-bromomesitol in trifluoromethanesulfonic acid and, similarly, 2,4,6-tribromo-4-methylcyclohexa-2,5-dienone rearranges to 2,3,6-tribromo-4-methylphenol.Under appropriate conditions debromination of bromodienones is competitive with rearrangement.Tetramethylammonium bromide in trifluoromethanesulfonic acid is an effective reagent for isomerization and disproportionation of bromophenols.Tetramethylammonium iodide in trifluoromethanesulfonic acid is an effective reagent for selective debromination of bromophenols at the ortho and para position.
- Fischer, Alfred,Henderson, George Narayanan
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p. 1045 - 1052
(2007/10/02)
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