- Nickel-Catalyzed Amination of Aryl Chlorides with Amides
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A nickel-catalyzed amination of aryl chlorides with diverse amides via C-N bond cleavage has been realized under mild conditions. A broad substrate scope with excellent functional group tolerance at a low catalyst loading makes the protocol powerful for synthesizing various aromatic amines. The aryl chlorides could selectively couple to the amino fragments rather than the carbonyl moieties of amides. Our protocol complements the conventional amination of aryl chlorides and expands the usage of inactive amides.
- Li, Jinpeng,Huang, Changyu,Wen, Daheng,Zheng, Qingshu,Tu, Bo,Tu, Tao
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supporting information
p. 687 - 691
(2021/01/09)
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- Photoarylation of Pyridines Using Aryldiazonium Salts and Visible Light: An EDA Approach
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A metal-free methodology for the photoarylation of pyridines, in water, is described giving 2 and 4-arylated-pyridines in yields up to 96percent. The scope of the aryldiazonium salts is presented showing important results depending on the nature and position of the substituent group in the diazonium salt, that is, electron-donating or electron-withdrawing in the ortho, meta, or para positions. Further heteroaromatics were also successfully photoarylated. Mechanistic studies and comparison between our methodology and similar metal-catalyzed procedures are presented, suggesting the occurrence of a visible-light EDA complex which generates the aryl radical with no need for an additional photocatalyst.
- Bartolomeu, Aloisio De A.,Brocksom, Timothy J.,De Oliveira, Kleber T.,No?l, Timothy,Silva, Rodrigo C.
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- Monoamine Oxidase (MAO-N) Whole Cell Biocatalyzed Aromatization of 1,2,5,6-Tetrahydropyridines into Pyridines
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A sustainable MAO-N biocatalyzed process for the synthesis of pyridines from aliphatic tetrahydropyridines (THP) has been developed. Pyridine compounds were synthesized under mild reaction conditions and with high conversion, exploiting MAO-N whole cells as aromatizing biocatalysts. The kinetic profile of the whole cell biocatalytic transformation was finally investigated via in situ 19F NMR.
- Toscani, Anita,Risi, Caterina,Black, Gary W.,Brown, Nicola L.,Shaaban, Ali,Turner, Nicholas J.,Castagnolo, Daniele
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p. 8781 - 8787
(2018/09/06)
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- Radical Arylation of Anilines and Pyrroles via Aryldiazotates
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The radical arylation of anilines and pyrroles can be achieved under transition-metal- and catalyst-free conditions by using aryldiazotates in strongly alkaline aqueous solutions. The aryldiazotates act as protected diazonium ions, which do not undergo azo coupling with electron-rich aromatic substrates, but can still serve as an aryl radical source at slightly elevated temperatures. Based on an improved preparation of aryldiazotates in aqueous solution, homolytic aromatic substitutions of anilines and pyrroles were conducted with good overall yields and high regioselectivity. Moreover, DFT calculations provided further mechanistic insights.
- Hofmann, Josefa,Gans, Eva,Clark, Timothy,Heinrich, Markus R.
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p. 9647 - 9656
(2017/07/22)
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- Discovery of an in Vivo Tool to Establish Proof-of-Concept for MAP4K4-Based Antidiabetic Treatment
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Recent studies in adipose tissue, pancreas, muscle, and macrophages suggest that MAP4K4, a serine/threonine protein kinase may be a viable target for antidiabetic drugs. As part of the evaluation of MAP4K4 as a novel antidiabetic target, a tool compound,
- Ammirati, Mark,Bagley, Scott W.,Bhattacharya, Samit K.,Buckbinder, Leonard,Carlo, Anthony A.,Conrad, Rebecca,Cortes, Christian,Dow, Robert L.,Dowling, Matthew S.,El-Kattan, Ayman,Ford, Kristen,Guimar?es, Cristiano R. W.,Hepworth, David,Jiao, Wenhua,Laperle, Jennifer,Liu, Shenping,Londregan, Allyn,Loria, Paula M.,Mathiowetz, Alan M.,Munchhof, Michael,Orr, Suvi T. M.,Petersen, Donna N.,Price, David A.,Skoura, Athanasia,Smith, Aaron C.,Wang, Jian
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supporting information
p. 1128 - 1133
(2015/11/24)
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- Encapsulation enhanced dimerization of a series of 4-aryl-N- methylpyridinium derivatives in water: New building blocks for self-assembly in aqueous media
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The construction of supramolecular systems in aqueous media is still a great challenge owing to the limited sources of building blocks. In this study, a series of 4-aryl-N-methylpyridinium derivatives have been synthesized. They formed very stable host-gu
- Zhang, Ying,Zhou, Tian-You,Zhang, Kang-Da,Dai, Jin-Ling,Zhu, Yuan-Yuan,Zhao, Xin
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supporting information
p. 1530 - 1534
(2014/06/09)
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- Triarylbismuthanes as threefold aryl-transfer reagents in regioselective cross-coupling reactions with bromopyridines and quinolines
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Cross-coupling studies using bromopyridines and bromoquinolines with triarylbismuths as threefold coupling reagents in substoichiometric amounts under Pd-catalysed conditions are disclosed. The reactivity was high with both mono- and dibromopyridyl substrates, and mono- and bis-couplings were carried out regioselectively. A library of monoaryl and diaryl pyridines was formed in high yields. A one-pot strategy provided a simple and straightforward synthesis of both symmetrical and unsymmetrical diarylpyridines. Arylations of 2-bromo- and 3-bromoquinolines were achieved with triarylbismuth reagents. This study demonstrates that triarylbismuths may be used as threefold arylating reagents for the synthesis of aryl pyridines and quinolines through couplings with bromopyridines and bromoquinolines under Pd-catalysed conditions. Copyright
- Rao, Maddali L.N.,Dhanorkar, Ritesh J.
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supporting information
p. 5214 - 5228
(2014/10/15)
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- Synthesis of Vinylphenylpyridine and Living Anionic Polymerization
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Provided are a vinyl-biphenylpyridine monomer and a polymer thereof. More particularly, the present invention provides a vinyl-biphenylpyridine monomer having a side chain of pyridine or phenylpyridine as a functional group, a homopolymer of which molecul
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Page/Page column 6
(2009/05/29)
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- Gold(I)-catalyzed direct C-H arylation of pyrazine and pyridine with aryl bromides
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An efficient procedure for the direct C-H arylation of electron-poor aromatics such as pyrazine and pyridine with aryl bomides is described. In the presence of catalytic amount of Cy3PAuCl and with the use of t-BuOK as base, pyrazine undergoes the direct C-H arylation with aryl bromides at 100 °C, and the yields of the arylated products depend on the nature of aryl bromides. In the cases of electron-rich aryl bromides used, the arylated pyrazines can be obtained in good to high yields. For electron-poor aryl bromides, the addition of AgBF4 is the crucial point to accelerate the coupling reaction to give the arylated products in moderate yields. Pyridine also reacts with electron-rich aryl bromides catalyzed by Cy3PAuCl to give a mixture of arylated regioisomers in moderate yield. However, in order to realize the direct C-H arylation of pyridine with electron-poor aryl bromides, the addition of silver salt as additive and a milder reaction temperature (60 °C) are required.
- Li, Ming,Hua, Ruimao
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supporting information; experimental part
p. 1478 - 1481
(2009/06/08)
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- Vesicular monoamine transporter substrate/inhibitor activity of MPTP/MPP+ derivatives: A structure-activity study
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The active metabolite of 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP), N-methyl-4-phenylpyridinium (MPP+), selectively destroys the dopaminergic neurons and induces the symptoms of Parkinson's disease. Inhibition of mitochondrial complex
- Wimalasena, D. Shyamali,Perera, Rohan P.,Heyen, Bruce J.,Balasooriya, Inoka S.,Wimalasena, Kandatege
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p. 760 - 768
(2008/09/19)
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- SYNTHESIS OF VINYLPHENYLPYRIDINE AND LIVING ANIONIC POLYMERIZATION
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Provided are a vinyl-biphenylpyridine monomer and a polymer thereof. More particularly, the present invention provides a vinyl-biphenylpyridine monomer having a side chain of pyridine or phenylpyridine as a functional group, a homopolymer of which molecul
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Page/Page column 9
(2010/11/29)
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- Arylpiperaszine derivatives, to the process for the production thereof and to the use thereof as therapeutic agents
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The invention relates to compounds of the general formula (I): to the process for preparing them, and to the use thereof as a therapeutic agent.
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Page/Page column 21
(2008/06/13)
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- o-Iodoxybenzoic Acid (IBX) as a Viable Reagent in the Manipulation of Nitrogen- and Sulfur-Containing Substrates: Scope, Generality, and Mechanism of IBX-Mediated Amine Oxidations and Dithiane Deprotections
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o-Iodoxybenzoic acid (IBX), a highly versatile hypervalent iodine(V) reagent, was found to efficiently mediate the dehydrogenation of amines in addition to facilitating the oxidative cleavage of dithioacetals and dithioketals. Through the development of relevant IBX-based protocols, a plethora of useful synthetic intermediates, including imines, oximes, ketones, and aromatic N-heterocycles, were found to be readily accessible under notably mild conditions. Further investigation of these transformations led to the elucidation of valuable mechanistic details, resulting in the conclusion that they proceed via ionic rather than single electron transfer (SET) pathways.
- Nicolaou,Mathison, Casey J. N.,Montagnon, Tamsyn
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p. 5192 - 5201
(2007/10/03)
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- New reactions of IBX: Oxidation of nitrogen- and sulfur-containing substrates to afford useful synthetic intermediates
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New reactions for the synthetic toolbox: 2-lodoxybenzoic acid (IBX) was employed to access a diverse array of useful synthetic intermediates. Among other transformations, the developed chemistry converts amines into imines, dithianes into carbonyl groups, N-heterocycles into N-heteroaromatic compounds, and hydroxylamines into oximes in high yields.
- Nicolaou,Mathison, Casey J. N.,Montagnon, Tamsyn
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p. 4077 - 4082
(2007/10/03)
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- Directed deprotonation-transmetalation as a route to substituted pyridines
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matrix presented Regioselective C-4 deprotonation of 3-bromopyridine, followed by Li/Zn transmetalation and Pd-mediated coupling processes, provides a flexible entry to 4-substituted and 3,4-disubstituted pyridines. Application of a similar sequence to 2-
- Karig, Gunter,Spencer, James A.,Gallagher, Timothy
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p. 835 - 838
(2007/10/03)
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- Syntheses and photophysical properties of some 4-arylpyridinium salts
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A number of 4-arylpyridines, many methoxy substituted, were prepared by an efficient two-step method involving aryl Grignard addition to 1-methyl-4-piperidone and direct aromatization of the resulting 4-aryl-4-piperidinols. The pyridines were N-alkylated to give sulfonate salts desired for their fluorescent properties. Study of selected compounds as laser dyes revealed several structures to be efficient dyes lasing in the 530-550 nm range. Two new diazaquaterphenyls were prepared and were quaternized. These salts exhibited intense fluorescence in the 420-450 nm range, but would not lase. A phenolic azaterphenyl suitably substituted for excited state intramolecular proton transfer (ESIPT) did not fluoresce at all.
- Kelley,Ansu,Budisusetyo,Ghiorghis,Qin,Kauffman
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- THE PYRIDYL CATION AS A REACTIVE INTERMEDIATE IN THE PHOTOREACTION OF IODOPYRIDINES WITH BENZENES
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The electrophilic behavior of the reactive entity in the photosubstitution of benzenes with 2-iodopyridine was found to be ascribable to the intermediary 2-pyridyl cation, rather than the electrophilic 2-pyridyl radical.
- Ohkura, Kazue,Seki, Koh-ichi,Terashima, Masanao,Kanaoka, Yuichi
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p. 3433 - 3436
(2007/10/02)
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- 4-(1-Chlorocyclohex-3-enyl)pyridines and preparation of 1-alkyl-1,4-dihydro-4-oxo-7-(4-pyridyl)-3-quinolinecarboxylic acid
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A 4-(1-chlorovinyl)pyridine, preferably 4-(1-chlorovinyl)pyridine itself, is reacted with a butadiene, preferably chloroprene, to prepare a 4-(1-chlorocyclohex-3-enyl)pyridine. The preferred products are useful as intermediates in the preparation of antibacterial 1-alkyl-1,4-dihydro-4-oxo-7-pyridinyl-3-quinolinecarboxylic acids.
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- Studies on Tertiary Amine Oxides. LXXVII. The Pseudo-Gomberg Reaction of 4- and 2-Aminopyridine 1-Oxides
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The 1-oxido-4-pyridyl radical generated by the reaction of 4-aminopyridine 1-oxide with amyl nitrite reacted smoothly with aromatic hydrocarbons, including five-membered heterocycles, i.e. thiophene, fyran and pyrrole, to give the arylated products when acetic acid was used as the solvent.The relative rates of reaction with the 1-oxido-4-pyridyl radical indicated that this radical is electrophilic, and this finding was supported by a comparison of molecular orbital energy levels. 2-Aminopyridine 1-oxide also undergoes a similar reaction.Keywords - pyridine N-oxide; Gomberg reaction; phenylpyridine; thienylpyridine; furylpyridine; 1-methanesulfonyl-pyrrolylpyridine; 1-oxido-4-pyridyl radical; molecular orbital; highperformance liquid chromatography
- Saeki, Seitaro,Kondo, Sachiko,Hayashi, Takaaki,Hamana, Masatomo
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p. 1780 - 1789
(2007/10/02)
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- Phase-Transfer-Catalyzed Gomberg-Bachmann Synthesis of Unsymmetrical Biarenes: A Survey of Catalysts and Substrates
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Two problems have hindered the Gomberg-Bachmann (GB) and Pschorr reactions of arenediazonium cations: the instability of the arenediazonium salts and side reactions.Arenediazonium tetrafluoroborate and hexafluorophosphate salts can be prepared in high yield and purity and can be stored safely.Unfortunately, these salts are insoluble in most nonpolar organic solvents.Crown ether complexation or other phase-transfer (pt) catalytic methodology can ameliorate this situation, and reactions conducted by the approaches outlined herein often afforded coupling or cyclization products in high yield and corresponding purity.The use of crown ethers, quarternary 'onium salts, lipophilic carboxylic acid salts, and even the polar cosolvent acetonitrile increase the utility of the ptGB reaction dramatically.Sixty examples of couplings are reported along with an assessment of selectivities.A number of examples are also presented of phase-transfer-type Pschorr cyclizations.In the latter case, the use of potassium superoxide, KO2, is introduced to suppress indazole formation.
- Beadle, James R.,Korzeniowsky, Stephen H.,Rosenberg, David E.,Garcia-Slanga, Blanche J.,Gokel, George W.
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p. 1594 - 1603
(2007/10/02)
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- Synthetic Applications of N-N Linked Heterocycles. Part 7. The Preparation of 4-Alkyl- and 4-Aryl-pyridines by Regiospecific Attack of Grignard Reagents γ to Quaternary Nitrogen in N-(2,6-Dimethyl-4-oxopyridin-1-yl)pyridinium Salts
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N-(2,6-Dimethyl-4-oxopyridin-1-yl)pyridinium salts (4), new reagents for the regiospecific synthesis of 4-substituted pyridines, give moderate to high yields of 4-alkyl- and 4-aryl-pyridines (8) - (10) on reaction with Grignard reagents.The scope and limitations on the reaction, which proceeds via 1,4-dihydro-intermediates (5) - (7), are explored.No 2-substituted pyridines were detected.Some reactions with organolithium compounds are also described.
- Katritzky, Alan R.,Beltrami, Hector,Sammes, Michael P.
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p. 2480 - 2484
(2007/10/02)
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