- Minimization of Back-Electron Transfer Enables the Elusive sp3 C?H Functionalization of Secondary Anilines
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Anilines are some of the most used class of substrates for application in photoinduced electron transfer. N,N-Dialkyl-derivatives enable radical generation α to the N-atom by oxidation followed by deprotonation. This approach is however elusive to monosubstituted anilines owing to fast back-electron transfer (BET). Here we demonstrate that BET can be minimised by using photoredox catalysis in the presence of an exogenous alkylamine. This approach synergistically aids aniline SET oxidation and then accelerates the following deprotonation. In this way, the generation of α-anilinoalkyl radicals is now possible and these species can be used in a general sense to achieve divergent sp3 C?H functionalization.
- Zhao, Huaibo,Leonori, Daniele
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supporting information
p. 7669 - 7674
(2021/03/08)
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- Porous polymeric ligand promoted copper-catalyzed C-N coupling of (hetero)aryl chlorides under visible-light irradiation
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A porous polymeric ligand (PPL) has been synthesized and complexed with copper to generate a heterogeneous catalyst (Cu@PPL) that has facilitated the efficient C-N coupling with various (hetero)aryl chlorides under mild conditions of visible-light irradiation at 80 °C (58 examples, up to 99% yields). This method could be applied to both aqueous ammonia and substituted amines, and is compatible to a variety of functional groups and heterocycles, as well as allows tandem C-N couplings with conjunctive dihalides. Furthermore, the heterogeneous characteristic of Cu@PPL has enabled a straightforward catalyst separation in multiple times of recycling with negligible catalytic efficiency loss by simple filtration, affording reaction mixtures containing less than 1 ppm of Cu residue. [Figure not available: see fulltext.]
- Wang, Erfei,Chen, Kaixuan,Chen, Yinan,Zhang, Jiawei,Lin, Xinrong,Chen, Mao
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- Method for preparing amine through catalytic reduction of nitro compound by cyclic (alkyl) (amino) carbene chromium complex
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The cyclic (alkyl) (amino) carbene chromium complex is prepared from corresponding ligand salt, alkali and CrCl3 and used for catalyzing pinacol borane to reduce nitro compounds in an ether solvent under mild conditions to generate corresponding amine. The method for preparing amine has the advantages of cheap and accessible raw materials, mild reaction conditions, wide substrate application range, high selectivity and the like, and is simple to operate.
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Paragraph 0015
(2021/04/17)
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- Cyclic (Alkyl)(amino)carbene Ligand-Promoted Nitro Deoxygenative Hydroboration with Chromium Catalysis: Scope, Mechanism, and Applications
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Transition metal catalysis that utilizes N-heterocyclic carbenes as noninnocent ligands in promoting transformations has not been well studied. We report here a cyclic (alkyl)(amino)carbene (CAAC) ligand-promoted nitro deoxygenative hydroboration with cost-effective chromium catalysis. Using 1 mol % of CAAC-Cr precatalyst, the addition of HBpin to nitro scaffolds leads to deoxygenation, allowing for the retention of various reducible functionalities and the compatibility of sensitive groups toward hydroboration, thereby providing a mild, chemoselective, and facile strategy to form anilines, as well as heteroaryl and aliphatic amine derivatives, with broad scope and particularly high turnover numbers (up to 1.8 × 106). Mechanistic studies, based on theoretical calculations, indicate that the CAAC ligand plays an important role in promoting polarity reversal of hydride of HBpin; it serves as an H-shuttle to facilitate deoxygenative hydroboration. The preparation of several commercially available pharmaceuticals by means of this strategy highlights its potential application in medicinal chemistry.
- Zhao, Lixing,Hu, Chenyang,Cong, Xuefeng,Deng, Gongda,Liu, Liu Leo,Luo, Meiming,Zeng, Xiaoming
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supporting information
p. 1618 - 1629
(2021/01/25)
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- Hydroboration reduction reaction of aromatic nitro compounds without transition metal catalysis
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The invention relates to a hydroboration reduction reaction of aromatic nitro compounds without transition metal catalysis. According to the method, triethyl boron and potassium tert-butoxide are used as catalysts for the first time, and an aromatic nitro compound and pinacol borane which is low in price and easy to obtain can be conveniently catalyzed to be subjected to a hydroboration reduction reaction under mild conditions to prepare aromatic amine products. Compared with a traditional method, the method generally has the advantages that the catalyst is cheap and easy to obtain, operation is convenient, and reaction is safe. The selective hydroboration reduction reaction of the non-transition metal reagent catalyzed aromatic nitro compound and pinacol borane is realized for the first time, and a practical new reaction strategy is provided for laboratory preparation or industrial production of aromatic amine products.
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Paragraph 0006; 0061-0064
(2021/07/31)
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- ARYL-PHOSPHORUS-OXYGEN COMPOUND AS EGFR KINASE INHIBITOR
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Disclosed is a class of new aryl-phosphorus-oxygen compounds as shown in formula (I) as EGFR kinase inhibitors, and pharmaceutically acceptable salts thereof.
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Paragraph 0230; 0231
(2020/06/16)
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- Aromatic amine compound synthesis method
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The invention discloses an aromatic amine compound synthesis method which is characterized in that the method is implemented according to any of two methods. The first method includes the steps: mixing an alkyl aromatic compound with a general formula (I) and a nitrogen-containing compound with a general formula (II); performing reaction on mixture under an oxidizing agent and an organic solvent to obtain an aromatic amine compound with a general formula (III). The second method includes the steps: mixing an aromatic alcohol derivative with a general formula (I') and the nitrogen-containing compound with the general formula (II); performing reaction on mixture under an acid additive and an organic solvent to prepare the aromatic amine compound with the general formula (III). According to the method, a lot of alkyl aromatic compounds or aromatic alcohol derivatives firstly serve as raw materials, and the raw materials are reacted to generate the aromatic amine compound without the action of metal catalysis. Compared with a traditional synthesis method, the synthesis method has the advantages that the method is high in yield and simple in condition, waste discharging amount is less,metal participation is omitted, a reaction device is simple, industrial production is easily achieved and the like. The method has a wide application prospect.
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Paragraph 0255-0257
(2019/01/23)
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- Simple Nickel Salts for the Amination of (Hetero)aryl Bromides and Iodides with Lithium Bis(trimethylsilyl)amide
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Recent developments in the chemistry of C-N bond formation and the synthesis of anilines have allowed for the use of first-row transition metals to catalyze these transformations. Much of the progress in this area has been driven by comprehensive screening for privileged/tailored ligands, which can be costly and not readily available in a research laboratory setting. In this communication we report a protocol in which simple nickel salts catalyze the C-N cross-coupling reaction between (hetero)aryl bromides and iodides with lithium bis(trimethylsilyl)amide without the need for any additive ligand. This method is amenable to low nickel catalyst loadings (1%) as well as gram-scale reactions. Because of the good functional group tolerance and compatibility with heterocyclic moieties, this method is useful for academic laboratory settings where access to tailored ligands and noble-metal catalysts could be challenging.
- Martinez, Gabriel Espinosa,Nugent, Joseph W.,Fout, Alison R.
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supporting information
p. 2941 - 2944
(2018/09/21)
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- A comparative reactivity survey of some prominent bisphosphine nickel(II) precatalysts in C-N cross-coupling
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The synthesis and characterization of the new air-stable precatalyst (L1)Ni(o-tol)Cl (C1; where L1 = JosiPhos CyPF-Cy) is reported, along with the results of a comparative reactivity survey involving C1 and analogous PAd-DalPhos- and DPPF-containing precatalysts (C2 and C3, respectively) in representative nickel-catalyzed C(sp2)-N cross-coupling reactions. Precatalyst C1 was found to be competitive with, and in some cases complementary to, C2 in the monoarylation of ammonia and primary alkylamines with (hetero)aryl chlorides, including in otherwise challenging room temperature transformations. (Pseudo)halide comparison studies involving the cross-coupling of furfurylamine at room temperature revealed that in contrast to C2 precatalyst C1 performs less effectively with aryl bromides. Whereas C3 was found to be ineffective for such transformations, this DPPF-derived precatalyst proved superior to C1 and C2 in reactions involving the secondary dialkylamine test substrate morpholine.
- Clark, Jillian S. K.,Lavoie, Christopher M.,MacQueen, Preston M.,Ferguson, Michael J.,Stradiotto, Mark
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supporting information
p. 3248 - 3254
(2016/10/09)
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- Nickel-catalyzed monoarylation of ammonia
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Structurally diverse (hetero)aryl chloride, bromide, and tosylate electrophiles were employed in the Ni-catalyzed monoarylation of ammonia, including chemoselective transformations. The employed JosiPhos/[Ni(cod)2] catalyst system enables the use of commercially available stock solutions of ammonia, or the use of ammonia gas in these reactions, thereby demonstrating the versatility and potential scalability of the reported protocol. Proof-of-principle experiments established that air-stable [(JosiPhos)NiCl2] precatalysts can be employed successfully in such transformations. Lighten Up: The substrate scope of the title reaction includes (hetero)aryl chloride, bromide, and tosylate electrophiles. The versatility and potential scalability of the reported method is demonstrated by the use of either commercially available stock solutions of ammonia or ammonia gas.
- Borzenko, Andrey,Rotta-Loria, Nicolas L.,Macqueen, Preston M.,Lavoie, Christopher M.,McDonald, Robert,Stradiotto, Mark
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supporting information
p. 3773 - 3777
(2015/03/18)
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- Synthesis, structure-activity relationships, and anticonvulsant activities of 2-amino-4H-pyrido[3,2-e][1,3]thiazin-4-one derivatives as orally active AMPA receptor antagonists
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As part of a program aimed at discovering orally active 2-amino-3-(3-hydroxy-5-methyl-4-isoxazolyl)propionic acid (AMPA) receptor antagonists, we screened our compound library and identified 2-[allyl(4-methylphenyl)amino]-4H-pyrido[3,2-e][1,3]thiazin-4-on
- Inami, Hiroshi,Shishikura, Jun-Ichi,Yasunaga, Tomoyuki,Ohno, Kazushige,Yamashita, Hiroshi,Kato, Kota,Sakamoto, Shuichi
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p. 1788 - 1799
(2015/03/30)
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- Palladium-catalyzed amination of aryl chlorides and bromides with ammonium salts
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We report the palladium-catalyzed coupling of aryl halides with ammonia and gaseous amines as their ammonium salts. The coupling of aryl chlorides and ortho-substituted aryl bromides with ammonium sulfate forms anilines with higher selectivity for the primary arylamine over the diarylamine than couplings with ammonia in dioxane. The resting state for the reactions of aryl chlorides is different from the resting state for the reactions of aryl bromides, and this change in resting states is proposed to account for a difference in selectivities for reactions of the two haloarenes.
- Green, Rebecca A.,Hartwig, John F.
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supporting information
p. 4388 - 4391
(2015/01/08)
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- Mild and highly selective palladium-catalyzed monoarylation of ammonia enabled by the use of bulky biarylphosphine ligands and palladacycle precatalysts
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A method for the Pd-catalyzed arylation of ammonia with a wide range of aryl and heteroaryl halides, including challenging five-membered heterocyclic substrates, is described. Excellent selectivity for monoarylation of ammonia to primary arylamines was achieved under mild conditions or at rt by the use of bulky biarylphosphine ligands (L6, L7, and L4) as well as their corresponding aminobiphenyl palladacycle precatalysts (3a, 3b, and 3c). As this process requires neither the use of a glovebox nor high pressures of ammonia, it should be widely applicable.
- Cheung, Chi Wai,Surry, David S.,Buchwald, Stephen L.
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supporting information
p. 3734 - 3737
(2013/08/23)
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- Ligandless copper-catalyzed coupling of heteroaryl bromides with gaseous ammonia
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A range of different N- and S-containing heterocyclic bromides can be efficiently coupled with gaseous ammonia in the presence of copper(II) acetylacetonate [Cu(acac)2] as catalyst and in the absence of additional ligands. Unstable aminothiophenes and aminobenzothiophenes can be further reacted in situ to afford functionalized derivatives. Copyright
- Fantasia, Serena,Windisch, Johannes,Scalone, Michelangelo
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supporting information
p. 627 - 631
(2013/04/11)
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- AMINOPYRIMIDINE COMPOUNDS AND METHODS OF USE
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The invention relates to aminopyrimidine compounds useful for treating diseases mediated by polo-like kinase 1 (Plk1). The invention also relates to the therapeutic use of such aminopyrimidine compounds and compositions thereof in treating disease states associated with abnormal cell growth and unwanted cell proliferation.
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Page/Page column 27
(2010/11/08)
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- Electroreduction of 1-methyl 5-nitroindole, 5-nitrobenzofurane, and 5-nitrobenzothiophene in acidic and basic hydroorganic media: Generation and trapping of iminoquinone-type intermediates and electrosynthesis of ring-substituted amino derivatives
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Preparative electrolysis of 1-methyl-5-nitroindole (1b, X = NCH 3), 5-nitrobenzofurane (1c, X = O), and 5-nitrobenzothiophene (1d, X = S) at Hg, in acidic hydromethanolic media, leads to the formation of the corresponding 4-substituted amino derivatives 5, which result from the 100% regioselective addition to iminoquinone-type intermediate 4 of methanol or of any other good nucleophile present in the electrolytic solution. In acidic medium, the iminoquinonium intermediates 4b and 4c were trapped in a cycloaddition reaction with cyclopentadiene added to the electrolysis medium. The regiochemistry of the nucleophilic addition is discussed in light of AM1 calculations.
- Bouchard, Luc,Marcotte, Ian,Chapuzet, Jean Marc,Lessard, Jean
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p. 1108 - 1118
(2007/10/03)
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- Synthesis and molecular modeling of new 1-aryl-3-[4-arylpiperazin-1-yl]-1-propane derivatives with high affinity at the serotonin transporter and at 5-HT1A receptors
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It has been proposed that 5-HT1A receptor antagonists augment the antidepressant efficacy of selective serotonin (5-HT) reuptake inhibitors. In a search toward new and efficient antidepressants, 1-(aryl)-3-[4-arylpiperazin-1-yl]-1-propane molecular hybrids were designed, synthesized, and evaluated for 5-HT reuptake inhibition and 5-HT1A receptor affinity. The design was based in coupling structural moieties related to inhibition of serotonin reuptake, such as benzo[b]-thiophene derivatives to arylpiperazines, typical 5-HT1A receptor ligands. In binding studies, several compounds showed affinity at the 5-HT transporter and at 5-HT1A receptors. Molecular modeling studies predicted the pharmacophore elements required for high affinity binding and the features that enable to discriminate between agonist, partial agonist, or antagonist action at 5-HT1A receptors and 5-HT transporter inhibition. Solvent interactions in desolvation prior to the binding step along with enthalpy and enthropy compensations might be responsible to explain agonist, partial agonist, and antagonist character. Hydrogen-bonding capability seems to be important to break hydrogen interhelical hydrogen bonds or alternatively to form other bonds upon ligand binding. Partial agonists and antagonists are unable to do this as the full agonist, which interacts closely by long-range forces or directly. The compounds showing the higher affinity at both the 5-HT transporter (Ki 1A receptors (Ki 35S]GTPγS binding or to antagonize 8-hydroxy-2-di-n-propylamino-tetralin (8-OH-DPAT)-stimulated [35]GTPγS binding to rat hippocampal membranes, an index of agonist/antagonist action at 5-HT1A receptors, respectively. Compound 8g exhibited agonist activity (EC50 = 30 nM) in this assay, whereas compounds 7g and 8h,i behaved as weak partial agonists and 7h-j and 8j,1 antagonized the R(+)-8-OH-DPAT-stimulated GTPγS binding. Functional characterization was performed by measuring the antagonism to 8-OH-DPAT-induced hypothermia in mice.
- Orús, Lara,Pérez-Silanes, Silvia,Oficialdegui, Ana-M.,Martínez-Esparza, Javier,Del Castillo, Juan-C,Mourelle, Marisa,Langer, Thierry,Guccione, Salvatore,Donzella, Giuseppina,Krovat, Eva M.,Poptodorov, Konstantin,Lasheras, Berta,Ballaz, Santiago,Hervías, Isabel,Tordera, Rosa,Del Río, Joaquín,Monge, Antonio
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p. 4128 - 4139
(2007/10/03)
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- The synthesis of 5-hydroxy-2,3-dihydrobenzo(B)thiophene (1) via an efficient one step preparation of 5-nitro-benzo(B) thiophene-2-carboxylate (3A)
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The preparation of 5-hydroxy-2,3-dihydrobenzothiophene 1 from 5-nitro-benzothiophene-2-carboxylate 3a is described along with an efficient one pot synthesis of 3a.
- Zambias,Hammond
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p. 959 - 964
(2007/10/02)
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