- Monodentate Transient Directing Group-Assisted Palladium-Catalyzed Direct ortho-C-H Iodination of Benzaldehydes for Total Synthesis of Hernandial
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The first palladium-catalyzed direct o-C-H iodination of benzaldehydes was successfully developed with the assistance of commercially available 2,5-bis(trifluoromethyl)aniline as the optimal monodentate transient directing group (MonoTDG). Moderate to exc
- Chen, Xuerong,La, Ming,Liu, Dandan,Zhang, Fang-Lin,Zhou, Yirong
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supporting information
p. 9184 - 9188
(2021/11/30)
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- Iodine(III)-Mediated, Controlled Di- or Monoiodination of Phenols
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An oxidative procedure for the electrophilic iodination of phenols was developed by using iodosylbenzene as a nontoxic iodine(III)-based oxidant and ammonium iodide as a cheap iodine atom source. A totally controlled monoiodination was achieved by buffering the reaction medium with K3PO4. This protocol proceeds with short reaction times, at mild temperatures, in an open flask, and generally with high yields. Gram-scale reactions, as well as the scope of this protocol, were explored with electron-rich and electron-poor phenols as well as heterocycles. Quantum chemistry calculations revealed PhII(OH)·NH3 to be the most plausible iodinating active species as a reactive "I+" synthon. In light of the relevance of the iodoarene moiety, we present herein a practical, efficient, and simple procedure with a broad functional group scope that allows access to the iodoarene core unit.
- Satkar, Yuvraj,Yera-Ledesma, Luisa F.,Mali, Narendra,Patil, Dipak,Segura-Quezada, Luis A.,Ramírez-Morales, Perla I.,Solorio-Alvarado, César R.,Navarro-Santos, Pedro
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p. 4149 - 4164
(2019/04/30)
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- Regioselective Halogenation of Arenes and Heterocycles in Hexafluoroisopropanol
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Regioselective halogenation of arenes and heterocycles with N-halosuccinimides in fluorinated alcohols is disclosed. Under mild condition reactions, a wide diversity of halogenated arenes are obtained in good yields with high regioselectivity. Additionally, the versatility of the method is demonstrated by the development of one-pot sequential halogenation and halogenation-Suzuki cross-coupling reactions.
- Tang, Ren-Jin,Milcent, Thierry,Crousse, Benoit
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p. 930 - 938
(2018/01/28)
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- Copper-catalyzed domino reaction of carbodiimides and benzoic acid derivatives for the synthesis of quinazolinediones
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Quinazolinediones were obtained from 2-iodobenzoic acids and carbodiimide derivatives under mild reaction conditions via a copper-catalyzed domino reaction. The absence of an external base was essential to avoid the generation of amide by-products. Both alkyl- and aryl-substituted carbodiimides gave the corresponding quinazolinediones. However, the use of aryl-substituted carbodiimides resulted in low yields due to an undesired elimination process.
- Duangjan, Chanikan,Rukachaisirikul, Vatcharin,Saithong, Saowanit,Kaeobamrung, Juthanat
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supporting information
p. 3537 - 3540
(2018/08/29)
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- F- Nucleophilic-Addition-Induced [3 + 2] Annulation: Direct Access to CF3-Substituted Indenes
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An efficient [3 + 2] annulation of (2,2-difluorovinyl)-2-iodoarenes and internal alkynes was developed for the synthesis of 1-(trifluoromethyl)-1H-indenes. The success of this strategy hinges upon a well-balanced process for the generation of two transient reactive species, specifically trifluoroethylsilver and alkenylpalladium intermediates, in the same molecule, as well as a smooth transmetalation step, which delicately joins together these two different metallic intermediates.
- Tang, Hai-Jun,Zhang, Yu-Feng,Jiang, Yi-Wen,Feng, Chao
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supporting information
p. 5190 - 5193
(2018/09/12)
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- Synthesis of Functionalized Alkylidene Indanes and Indanones through Tandem Phosphine-Palladium Catalysis
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Densely functionalized alkylidene indanes and indanones can be prepared efficiently in one pot, in high yields with good stereoselectivities (in some cases exclusively the Z-isomer), through a route involving phosphine-catalyzed Michael addition followed
- Fan, Yi Chiao,Kwon, Ohyun
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supporting information
p. 2058 - 2061
(2015/05/20)
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- Palladium-catalyzed insertion of N-tosylhydrazones for the synthesis of isoindolines
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Isoindolines are synthesized by palladium-catalyzed coupling reaction of N-(2-iodobenzyl) anilines with α,β-unsaturated N-tosylhydrazones. The reaction has several potential advantages: (1) toleration of a wide range of functional groups, (2) easy to handle and with mild conditions, (3) enriches the isoindoline family, (4) two new bonds form in one step.
- Zhou, Ping-Xin,Luo, Jian-Yi,Zhao, Lian-Biao,Ye, Yu-Ying,Liang, Yong-Min
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supporting information
p. 3254 - 3256
(2013/05/08)
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- Total synthesis of six 3,4-unsubstituted coumarins
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In this article we describe a new methodology for the total synthesis of 3,4-unsubstituted coumarins from commercially available starting materials. Six examples were prepared, including five naturally occurring coumarins-7-hydroxy- 6,8-dimethoxycoumarin (isofraxidin), 7-hydroxy-6-methoxycoumarin (scopoletin), 6,7,8-trimethoxycoumarin, 6,7-dimethoxycoumarin (scoparone), and 7,8-dihydroxycoumarin (daphnetin) and one synthetic coumarin, 7-hydroxy-6-ethoxycoumarin. Moreover, five important o-hydroxybenzaldehyde intermediates were also obtained, namely 2,4-dihydroxy-3,5- dimethoxybenzaldehyde, 2,4-dihydroxy-5-methoxybenzaldehyde, 5-ethoxy-2,4- dihydroxybenzaldehyde, 2-hydroxy-3,4,5-trimethoxybenzaldehyde, and 2-hydroxy-4,5-dimethoxybenzaldehyde. The method developed herein involves just three or four steps and allows for the rapid synthesis of these important molecules in excellent yields. This is the first synthesis of 6,7,8-trimethoxycoumarin and 7-hydroxy-6-ethoxycoumarin.
- Gao, Wenqing,Li, Qingyong,Chen, Jian,Wang, Zhichao,Hua, Changlong
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p. 15613 - 15623
(2014/01/17)
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- FUSED RING ANALOGUES OF ANTI-FIBROTIC AGENTS
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The present invention relates to arylcarbonyl and heteroarylcarbonyl anthranilate compounds that may be useful as anti-fibrotic agents. The present invention also relates to methods for their preparation, pharmaceutical compositions containing these compounds and uses of these compounds in the treatment disorders.
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Page/Page column 92-93
(2011/05/06)
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- Synthesis of isohasubanan alkaloids via enantioselective ketone allylation and discovery of an unexpected rearrangement
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A synthesis of the hasubanan alkaloids hasubanonine, runanine, and aknadinine via a unified route was attempted. Construction of key phenanthrene intermediates by a Suzuki coupling-Wittig olefination-ring-closing metathesis sequence allowed a convergent a
- Nielsen, Daniel K.,Nielsen, Laura L.,Jones, Spencer B.,Toll, Lawrence,Asplund, Matthew C.,Castle, Steven L.
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scheme or table
p. 1187 - 1199
(2009/07/25)
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- IBX-I2 redox couple for facile generation of IOH and I +: Expedient protocol for iodohydroxylation of olefins and iodination of aromatics
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(Chemical Equation Presented) IBX is readily reduced to IBAin the presence of molecular iodine in DMSO to generate hypoiodous acid (IOH), which reacts with a variety of olefins as well as R, β-unsaturated ketones leading to their respective iodohydrins with anti stereochemistry. The same redox chemistry in acetonitrile containing TFA produces iodonium ions for facile iodination of a variety of aromatic compounds in respectable isolated yields.
- Moorthy, Jarugu Narasimha,Senapati, Kalyan,Kumar, Sarvesh
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supporting information; experimental part
p. 6287 - 6290
(2009/12/08)
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- Facile total synthesis of benzo[b]furan natural product XH-14
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An efficient and practical total synthesis of benzo[b]furan natural product XH-14 is demonstrated in nine steps from vanillin. Introduction of iodide substituents in the reaction including optimization of the reaction sequences is essential for the successful synthesis of XH-14. Sonogashira coupling with iodobenzene, iodine-induced cyclization, Wittig reaction, and formylation are critical in the high-yield total synthesis of XH-14. Copyright Taylor & Francis Group, LLC.
- Bang, Hyun Bae,Han, Su Young,Choi, Da Hye,Yang, Deok Mo,Hwang, Jung Woon,Lee, Hyun Suck,Jun, Jong-Gab
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body text
p. 506 - 515
(2009/06/28)
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- Novel trifluoromethylepinephrine compounds and methods of making and using thereof
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Disclosed herein are trifluoromethylepinephrine compounds having the following structural formula (I) wherein R1-R5 are each independently selected from the group consisting of H, alkyl, alkoxyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl, acyl, thioacyl, sulfonyl mercapto, alkylthio, carboxy, amino, alkylamino dialkylamino, carbamoyl, arylthio, and heteroarylthio; wherein X, Y, and Z are each independently selected from the group consisting of H or trifluoromethyl with the proviso that at least one of which is trifluoromethyl. Also disclosed are pharmaceutical compositions comprising the trifluoromethylepinephrine compounds and methods of making and using thereof. Novel trifluoroepinephrine intermediates are also disclosed.
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- [5]Helicenes by tandem radical cyclisation
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A new and rapid approach to [5]helicenes is described. A central feature is the use of a sequential, non-reducing radical cyclisation reaction of (Z,Z)-1,4-bis(2-iodostyryl)benzene derivatives, viz. 3→1, mediated by tributyltin hydride.
- Harrowven, David C.,Nunn, Michael I.T.,Fenwick, David R.
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p. 7345 - 7347
(2007/10/03)
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- A Convenient Strategy for the Synthesis of 4,5-Bis(o-haloaryl)isoxazoles
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A series of new 1,2-bis(o-haloaryl)ethanones is efficiently prepared and applied to the synthesis of 4,5-bis(o-haloaryl)isoxazoles. Isolation of intermediate hydroxyisoxazolines, which are structurally examined, provides a definitive proof for a heterocyclization mechanism based on an amine exchange process. The isolation and X-ray crystallographic studies of significant side products such as benzamides and triarylpropionitriles are also described.
- Olivera, Roberto,SanMartin, Raul,Dominguez, Esther,Solans, Xabier,Urtiaga, Miren Karmele,Arriortua, Maria Isabel
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p. 6398 - 6411
(2007/10/03)
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- Synthesis of ring-halogenated 3,4-dimethoxyphenylethanolamine derivatives: New β-adrenoceptor antagonists
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A series of ring-halogenated derivatives (bromo and iodo) of [2-(3,4-dimethoxyphenyl)-2-hydroxyethyl]isopropylamine and [2-(3,4-dimethoxyphenyl)-2-methoxyethyl]isopropylamine was synthesized from benzaldehyde derivatives, via (halo-3,4-dimethoxyphenyl)ethylene oxide compounds. The compounds were tested as β-adrenoceptor antagonists on isolated guinea-pig tracheal (β2-adrenoceptors) and guinea-pig atrial (β1-adrenoceptors) muscle strips. Compounds halogenated in the 2-and 5-positions of the aromatic ring are potent β2-adrenoceptor antagonists, whereas halogenation of the 6-position of the aromatic ring leads to compounds which are weak β-adrenoceptor antagonists. β1-Selective drugs of very low potency were obtained when the β-hydroxyl group was replaced by a methoxy group.
- Venter, Daniel P.,Langenhoven, Jan H.
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- The asymmetric synthesis of aryltetralin lignans: (-)-isolariciresinol dimethyl ether and (-)-deoxysikkimotoxin
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The total asymmetric syntheses of (-)-isolariciresinol dimethyl ether (6) and (-)-deoxysikkimotoxin (7) have been carried out, in an attempt to exploit a synthetic strategy recently developed for the synthesis of (-)-deoxypodophyllotoxin (1, R1 = -CH2-, Ar = 3,4,5-trimethoxyphenyl). In so doing, a generalized method for the synthesis of aryltetralin lignans has been developed that should be applicable to a variety of substitution patterns and stereochemistries. A one-pot, 100% regio-selective reduction-lactonization procedure has been developed for the conversion of the ester 18b to (-)-deoxysikkimotoxin, which gave 93% isolated yield in that step.
- Coltart, Don M.,Charlton, James L.
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- Biphenyl derivatives, process for preparing the same and intermediates therefor
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Novel biphenyl derivatives of the formula: wherein R1 is a substituted or unsubstituted aminocarbonyl group, aminothiocarbonyl group, a substituted or unsubstituted lower alkoxycarbonyl group, cyano group, or a group of the formula: STR1 one or
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- A New Approach to the Synthesis of Peltogynoids, Natural Isochromenochromenes
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The (+/-)-trimethyl ether of the unusual isochromenochromene peltogynol 1 (R = OMe) and its ring skeleton 1 (R = H) have been synthesized via 6-endo intramolecular cyclisation of the radicals derived from the 3-(o-iodobenzyloxy)chromones 17 (R = OM
- Ahmad-Junan, S. Asiah,Whiting, Donald A.
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p. 675 - 678
(2007/10/02)
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- Synthesis of (+/-)-Trimethylpeltogynol via 6-endo Radical Cyclisation
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The (+/-)-trimethyl ether of the unusual heterocycle peltogynol (3; R= OMe), and its ring skeleton (9; R= H), have been synthesised via 6-endo intracyclisation of the radical derived from the iodides (8; R= H) and (8; R= OMe).
- Ahmad-Junan, S. Asiah,Whiting, Donald A.
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p. 418 - 419
(2007/10/02)
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