- Synthesis of 7-pentafluorophenyl-1 H -indole: An anion receptor for anion-π interactions
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7-Pentafluorophenyl-1H-indole has the potential to be a key compound for the investigation of anion-π interactions in solution. Unfortunately, it was not possible to obtain it by aryl-aryl coupling reaction. Finally, it has been prepared by Bartoli indole synthesis. The key compound as well as analogues were submitted to preliminary studies of anion binding. Single crystals of two key receptors were obtained. Georg Thieme Verlag Stuttgart New York.
- Sun, Zhan-Hu,Albrecht, Markus,Giese, Michael,Pan, Fangfang,Rissanen, Kari
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- Rh(iii)-catalyzed C-7 arylation of indolines with arylsilanes via C-H activation
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Site-selective synthesis of C-7 arylated indolines has been achieved via oxidative arylation of indolines with arylsilanes under Rh(iii)-catalyzed C-H activation of indolines by using CuSO4 as a co-oxidant. This transformation has been explored for a wide range of substrates under mild conditions.
- Luo, Haiqing,Xie, Qi,Sun, Kai,Deng, Jianbo,Xu, Lin,Wang, Kejun,Luo, Xuzhong
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- Intermolecular Nucleophilic Addition Reaction of a C-7 Anion from N -[Bis(dimethylamino)phosphoryl]indole to Electrophiles/Arynes: Synthesis of 7-Substituted Indoles
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A novel approach to the C-7 substitution of N-[bis(dimethylamino)phosphoryl]indole by nucleophilic addition of the corresponding C-7 carbanion to electrophiles or arynes is described. The directing group can be easily removed, providing a simple route to the synthesis of 7-functionalized indoles.
- Kaur, Amarjit,Kaur, Babaldeep,Kaur, Manjot,Sharma, Esha,Singh, Kamal Nain,Singh, Paramjit
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- Iron(II)-Catalyzed Aerobic Biomimetic Oxidation of N-Heterocycles
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Herein, an iron(II)-catalyzed biomimetic oxidation of N-heterocycles under aerobic conditions is described. The dehydrogenation process, involving several electron-transfer steps, is inspired by oxidations occurring in the respiratory chain. An environmentally friendly and inexpensive iron catalyst together with a hydroquinone/cobalt Schiff base hybrid catalyst as electron-transfer mediator were used for the substrate-selective dehydrogenation reaction of various N-heterocycles. The method shows a broad substrate scope and delivers important heterocycles in good-to-excellent yields.
- Manna, Srimanta,Kong, Wei-Jun,B?ckvall, Jan-E.
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supporting information
p. 13725 - 13729
(2021/09/08)
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- Catalytic C(sp2)?H amination reactions using dinickel imides
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C?H amination reactions are valuable transformations for the construction of C?N bonds. Due to their relatively high bond dissociation energies, C(sp2)?H bonds are generally not susceptible toward direct nitrene insertion, necessitating alternative mechanisms for C?H activation. Here, we report that cationic dinuclear (NDI)Ni2 (NDI = naphthyridine?diimine) complexes catalyze intramolecular nitrene insertions into aryl and vinyl C(sp2)? H bonds. Mechanistic studies suggest that a bridging imido ligand supported at a Ni2 site induces C?H activation by a 1,2-addition pathway to generate an azametallacyclic intermediate. This organometallic mechanism contrasts with the electrocyclization/1,2-shift mechanism proposed for analogous transformations using Rh2 catalysts. The implications of these mechanistic differences for the stereoselectivity and chemoselectivity of C?H amination are described.
- Andjaba, John M.,Powers, Ian G.,Uyeda, Christopher,Zeller, Matthias
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p. 3794 - 3801
(2020/11/23)
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- Preparation method of 7-phenylindole compound
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The invention discloses a preparation method of a 7-phenylindole compound. Indole is used as a starting raw material, under the condition that n-butyllithium is used as an alkali, a di-tert-butylphosphine guide group is introduced to the C1 site of an indole ring, a steric effect and a coordination effect are utilized to activate a carbon-hydrogen bond at the C7 site of the indole ring, and palladium acetate is adopted to catalyze an organic tin reagent to perform a carbon-carbon bond coupling reaction, so that arylation of the C7 site of the indole ring is realized; and by taking tetrabutylammonium fluoride as an alkaline condition, removing of the di-tert-butylphosphine guide group is carried out to obtain the 7-phenylindole compound. According to the method, halogenation does not need to be conducted at the C7 position of the indole ring in advance, the optimized reaction condition is mild, the substrate universality is good, the reaction yield is high, and the method is a new method for synthesizing the 7-phenylindole compound.
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- Synthesis of Seven-Membered Azepino[3,2,1- hi]indoles via Rhodium-Catalyzed Regioselective C-H Activation/1,8-Diazabicyclo[5.4.0]undec-7-ene-Catalyzed Intramolecular Amidation of 7-Phenylindoles in One Pot
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An unprecedented rhodium-catalyzed regioselective C-H activation/1,8-diazabicyclo[5.4.0]undec-7-ene-catalyzed intramolecular amidation of 7-arylindoles with diazomalonates is described that provides a straightforward route to seven-membered azepino[3,2,1-hi]indoles in good to excellent yields in one pot. A wide range of functional groups, including F, OMe, NPh2, SiMe3, Cl, CN, CHO, COMe, CO2Me, CF3, and NO2, were all well-tolerated.
- Yuan, Yumeng,Pan, Guoshuai,Zhang, Xiaofeng,Li, Buhong,Xiang, Shengchang,Huang, Qiufeng
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p. 14701 - 14711
(2019/11/19)
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- Expedient cobalt(II)-catalyzed site-selective C7-arylation of indolines with arylboronic acids
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Cobalt(ii)-catalyzed pyrimidyl directing group-assisted C7 arylation of indolines with arylboronic acids has been developed using Mn(OAc)2·4H2O as an oxidant. The use of cobalt(ii)-PCy3 as a catalyst and broad substrate scope are the important practical features.
- De, Pinaki Bhusan,Pradhan, Sourav,Banerjee, Sonbidya,Punniyamurthy, Tharmalingam
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p. 2494 - 2497
(2018/03/21)
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- Spatially isolated palladium in porous organic polymers by direct knitting for versatile organic transformations
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We report here a direct knitting Method for preparation of highly robust, effective while air- and moisture-tolerant, and readily recyclable three-dimensional (3D) porous polymer-Pd network (PPPd) from the widely used Pd(PPh3)4. Electro-beam induced Pd atom crystallization was observed for the first time in organic polymer and revealed the ultrafine dispersion of palladium atoms. Challenging types of Suzuki-Miyaura couplings, reductive coupling of aryl halides and oxidative coupling of arylboronic acid were successively catalyzed by PPPd in aqueous media. Also catalytically selective C–H functionalization reactions were achieved with orders of magnitude more efficient than conventional Pd homogeneous catalysts. The strategy developed here provides a practical method for easy-to-make yet highly efficient heterogeneous catalysis.
- Wang, Xinbo,Min, Shixiong,Das, Swapan K.,Fan, Wei,Huang, Kuo-Wei,Lai, Zhiping
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p. 101 - 109
(2017/10/06)
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- Direct and site-selective Pd(ii)-catalyzed C-7 arylation of indolines with arylsilanes
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The palladium-catalyzed oxidative arylation of indolines with arylsilanes at the C-7 position via C-H bond activation has been reported. This transformation has been applied to a wide range of substrates. It represents a facile access to C-7 arylated indolines, which can be conveniently transformed into C-7 arylated indoles.
- Luo, Haiqing,Liu, Haidong,Zhang, Zhipeng,Xiao, Yifan,Wang, Sihui,Luo, Xuzhong,Wang, Kejun
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p. 39292 - 39295
(2016/06/01)
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- Pyridazine N-Oxides as Precursors of Metallocarbenes: Rhodium-Catalyzed Transannulation with Pyrroles
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Pyridazine N-oxides are used for the first time as precursors of metallocarbenes. These nitrogen-rich heterocycles led to the discovery of a novel acceptor and donor-acceptor enalcarbenoids. The synthetic utility of these metallocarbenes was demonstrated in the rhodium-catalyzed denitrogenative transannulation of pyridazine N-oxides with pyrroles to the valuable alkyl, 7-aryl, and 7-styryl indoles. The transannulation strategy was applied to the synthesis of a potent anticancer agent.
- Kanchupalli, Vinaykumar,Joseph, Desna,Katukojvala, Sreenivas
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supporting information
p. 5878 - 5881
(2015/12/11)
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- Rapid synthesis of fused N-heterocycles by transition-metal-free electrophilic amination of arene C-H bonds
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We disclose an efficient and operationally simple protocol for the preparation of fused N-heterocycles starting from readily available 2-nitrobiaryls and PhMgBr under mild conditions. More than two dozen N-heterocycles, including two bioactive natural products, have been synthesized using this method. A stepwise electrophilic aromatic cyclization mechanism was proposed by DFT calculations. Controlled fusion: A transition-metal-free, low-temperature, and regioselective intramolecular amination of aromatic C(sp2)-H bonds provides fused N-heterocycles. This reaction is operationally simple and scalable (1-10 mmol) and the scope of substrates is wide (see scheme). Density functional calculations indicate that a stepwise electrophilic aromatic cyclization mechanism may be operative.
- Gao, Hongyin,Xu, Qing-Long,Yousufuddin, Muhammed,Ess, Daniel H.,Kuerti, Laszlo
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supporting information
p. 2701 - 2705
(2014/03/21)
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- Iridium-catalyzed, silyl-directed borylation of nitrogen-containing heterocycles
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Chemical Figure Presented Selective methods for the functionalization of indoles and other nitrogen heterocycles would provide access to the core structures of many natural products and pharmaceuticals. Although there are many methods and strategies for the synthesis of substituted indoles or functionalization of the azole ring, strategies for the selective functionalization of the benzo-fused portion of the indole skeleton, particularly the 7-position, are less common. We report a one-pot, iridium-catalyzed, silyl-directed C-H borylation of indoles at the 7-position. This process occurs in high yield with a variety of substituted indoles, and conversions of the 7-borylindole products to 7-aryl-, 7-cinnamyl-, and 7-haloindoles are demonstrated. The lr-catalyzed, silyl-directed C-H borylation also occurs with several other nitrogen heterocycles, including carbazole, phenothiazines, and tetrahydroquinoline. The utility of this methodology is highlighted by the one-pot synthesis of a member of the pyrrolophenanthrldone class of alkaloid natural products. Copyright
- Robbins, Daniel W.,Boebel, Timothy A.,Hartwig, John F.
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supporting information; experimental part
p. 4068 - 4069
(2010/05/01)
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- Phenylaminopropanol derivatives and methods of their use
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The present invention is directed to phenylaminopropanol derivatives of formulae I, II, and III: [image] or a pharmaceutically acceptable salt thereof, compositions containing these derivatives, and methods of their use for the prevention and treatment of conditions ameliorated by monoamine reuptake including, inter alia, vasomotor symptoms (VMS), sexual dysfunction, gastrointestinal and genitourinary disorders, chronic fatigue syndrome, fibromyalgia syndrome, nervous system disorders, and combinations thereof, particularly those conditions selected from the group consisting of major depressive disorder, vasomotor symptoms, stress and urge urinary incontinence, fibromyalgia, pain, diabetic neuropathy, schizophrenia, and combinations thereof.
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Page/Page column 48
(2010/11/26)
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- Palladium-catalyzed Suzuki-Miyaura cross-coupling reactions of potassium aryl- and heteroaryltrifluoroborates
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An extended study of the reactivity of potassium aryl- and heteroaryltrifluoroborates in Suzuki-Miyaura cross-coupling reactions is presented. The coupling of aryl- and electron-rich heteroaryltrifluoroborates with aryl and activated heteroaryl bromides proceeds readily under ligandless conditions. When deactivated aryl- and heteroaryltrifluoroborates are coupled with aryl and heteroaryl bromides and chlorides, a low loading (0.5-2%) of PdCl2(dppf)·CH2Cl2 efficiently catalyzes the reactions. Under either condition, reactions can generally be carried out in an open atmosphere.
- Molander, Gary A.,Biolatto, Betina
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p. 4302 - 4314
(2007/10/03)
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- Directed ortho metalation approach to C-7-substituted indoles. Suzuki-Miyaura cross coupling and the synthesis of pyrrolophenanthridone alkaloids
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(Matrix presented) Although the indole N-phosphinoyl derivative 4 undergoes n-BuLi deprotonation/electrophile quench to afford C-7-substituted products, its deprotection requires harsh conditions. On the other hand, the N-amide 12, upon sequential or one-pot C-2 metalation, silylation, C-7 metalation, and electrophile treatment, furnishes indoles 7 in good overall yields. In combination with the Suzuki-Miyaura protocol, C-7 aryl (heteroaryl)-substituted indoles 14 and 16 are obtained, including hippadine and pratosine, members of the pyrrolophenanthridone alkaloid family.
- Hartung, Christian G.,Fecher, Anja,Chapell, Brian,Snieckus, Victor
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p. 1899 - 1902
(2007/10/03)
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