- Iodine-Mediated Coupling of Cyclic Amines with Sulfonyl Hydrazides: an Efficient Synthesis of Vinyl Sulfone Derivatives
-
An efficient iodine-mediated coupling of cyclic amines with sulfonyl hydrazides is reported. This transformation opens a new route to the synthesis of vinyl sulfones derivatives, which is a common structural motif in natural products and pharmaceuticals. Tentative mechanistic studies suggest that this reaction is likely to involve a radical process.
- Rong, Xiaona,Guo, Jingwen,Hu, Zheqi,Huang, Lehao,Gu, Yugui,Cai, Yuepiao,Liang, Guang,Xia, Qinqin
-
supporting information
p. 701 - 708
(2020/12/30)
-
- Leaving Group Ability in Nucleophilic Aromatic Amination by Sodium Hydride-Lithium Iodide Composite
-
The methoxy group is generally considered as a poor leaving group for nucleophilic substitution reactions. This work verified the superior ability of the methoxy group in nucleophilic amination of arenes mediated by the sodium hydride and lithium iodide through experimental and computational approaches.
- Chiba, Shunsuke,Ong, Derek Yiren,Pang, Jia Hao,Takita, Ryo,Watanabe, Kohei
-
p. 393 - 398
(2020/01/23)
-
- Palladium Complexes Based on Ylide-Functionalized Phosphines (YPhos): Broadly Applicable High-Performance Precatalysts for the Amination of Aryl Halides at Room Temperature
-
Palladium allyl, cinnamyl, and indenyl complexes with the ylide-substituted phosphines Cy3P+?C?(R)PCy2 (with R=Me (L1) or Ph (L2)) and Cy3P+?C?(Me)PtBu2 (L3) were prepared and applied as defined precatalysts in C?N coupling reactions. The complexes are highly active in the amination of 4-chlorotoluene with a series of different amines. Higher yields were observed with the precatalysts in comparison to the in situ generated catalysts. Changes in the ligand structures allowed for improved selectivities by shutting down β-hydride elimination or diarylation reactions. Particularly, the complexes based on L2 (joYPhos) revealed to be universal precatalysts for various amines and aryl halides. Full conversions to the desired products are reached mostly within 1 h reaction time at room temperature, thus making L2 to one of the most efficient ligands in C?N coupling reactions. The applicability of the catalysts was demonstrated for aryl chlorides, bromides and iodides together with primary and secondary aryl and alkyl amines, including gram-scale applications also with low catalyst loadings of down to 0.05 mol %. Kinetic studies further demonstrated the outstanding activity of the precatalysts with TOF over 10.000 h?1.
- Tappen, Jens,Rodstein, Ilja,McGuire, Katie,Gro?johann, Angela,L?ffler, Julian,Scherpf, Thorsten,Gessner, Viktoria H.
-
supporting information
p. 4281 - 4288
(2020/03/13)
-
- General Paradigm in Photoredox Nickel-Catalyzed Cross-Coupling Allows for Light-Free Access to Reactivity
-
Self-sustained NiI/III cycles are established as a potentially general paradigm in photoredox Ni-catalyzed carbon–heteroatom cross-coupling reactions through a strategy that allows us to recapitulate photoredox-like reactivity in the absence of light across a wide range of substrates in the amination, etherification, and esterification of aryl bromides, the latter of which has remained, hitherto, elusive under thermal Ni catalysis. Moreover, the accessibility of esterification in the absence of light is especially notable because previous mechanistic studies on this transformation under photoredox conditions have unanimously invoked energy-transfer-mediated pathways.
- Nocera, Daniel G.,Qin, Yangzhong,Sun, Rui
-
supporting information
p. 9527 - 9533
(2020/04/08)
-
- Practical and regioselective amination of arenes using alkyl amines
-
The formation of carbon–nitrogen bonds for the preparation of aromatic amines is among the top five reactions carried out globally for the production of high-value materials, ranging from from bulk chemicals to pharmaceuticals and polymers. As a result of this ubiquity and diversity, methods for their preparation impact the full spectrum of chemical syntheses in academia and industry. In general, these molecules are assembled through the stepwise introduction of a reactivity handle in place of an aromatic C–H bond (that is, a nitro group, halogen or boronic acid) and a subsequent functionalization or cross-coupling. Here we show that aromatic amines can be constructed by direct reaction of arenes and alkyl amines using photocatalysis, without the need for pre-functionalization. The process enables the easy preparation of advanced building blocks, tolerates a broad range of functionalities, and multigram scale can be achieved via a batch-to-flow protocol. The merit of this strategy as a late-stage functionalization platform has been demonstrated by the modification of several drugs, agrochemicals, peptides, chiral catalysts, polymers and organometallic complexes.
- Ruffoni, Alessandro,Juliá, Fabio,Svejstrup, Thomas D.,McMillan, Alastair J.,Douglas, James J.,Leonori, Daniele
-
p. 426 - 433
(2019/05/01)
-
- Well-Designed N-Heterocyclic Carbene Ligands for Palladium-Catalyzed Denitrative C-N Coupling of Nitroarenes with Amines
-
The C-N bond formation is one of the fundamental reactions in organic chemistry, because of the widespread presence of amine moieties in pharmaceuticals and biologically active compounds. Palladium-catalyzed C-N coupling of haloarenes represents one of the most efficient approaches to aromatic amines. Nitroarenes are ideal alternative electrophilic coupling partners, since they are inexpensive and readily available. The denitration and cross-coupling using nitroarenes as the electrophilic partners is challenging, because of the low reactivity of the Ar-NO2 bond toward oxidative addition. We report here the C-N coupling of nitroarenes and amines using palladium/5-(2,4,6-triisopropylphenyl)imidazolylidene[1,5-a]pyridines as the catalyst. The ligands are readily available from commercial chemicals. The reaction shows broad substrate scope and functional group tolerance. The method is applicable to both aromatic and aliphatic amines, and many secondary and tertiary aromatic amines bearing various functional groups were obtained in high yields.
- Chen, Kai,Chen, Wanzhi,Chen, Wei,Liu, Miaochang,Wu, Huayue
-
p. 8110 - 8115
(2019/08/26)
-
- Synthesis of Arylamines via Aminium Radicals
-
Arylamines constitute the core structure of many therapeutic agents, agrochemicals, and organic materials. The development of methods for the efficient and selective construction of these structural motifs from simple building blocks is desirable but stil
- Svejstrup, Thomas D.,Ruffoni, Alessandro,Juliá, Fabio,Aubert, Valentin M.,Leonori, Daniele
-
p. 14948 - 14952
(2017/11/20)
-
- Nucleophilic Amination of Methoxy Arenes Promoted by a Sodium Hydride/Iodide Composite
-
A method for the nucleophilic amination of methoxy arenes was established by using sodium hydride (NaH) in the presence of lithium iodide (LiI). This method offers an efficient route to benzannulated nitrogen heterocycles. Mechanistic studies showed that the reaction proceeds through an unusual concerted nucleophilic aromatic substitution.
- Kaga, Atsushi,Hayashi, Hirohito,Hakamata, Hiroyuki,Oi, Miku,Uchiyama, Masanobu,Takita, Ryo,Chiba, Shunsuke
-
supporting information
p. 11807 - 11811
(2017/09/20)
-
- n-Butyllithium-mediated synthesis of N-aryl tertiary amines by reactions of fluoroarenes with secondary amines at room temperature
-
A simple and facile method for the synthesis of aromatic tertiary amines by amination of fluoroarenes with secondary amines in the presence of n-butyllithium at room temperature was reported.
- Lin, Yingyin,Li, Meng,Ji, Xinfei,Wu, Jingjing,Cao, Song
-
p. 1466 - 1472
(2017/02/18)
-
- An efficient heterogeneous ligand free C-N coupling reaction catalyzed by palladium supported on magnetic nanoparticles
-
The catalytic activity of palladium supported on magnetic nanoparticles in the amination coupling reaction of different nitrogen containing substrates with aryl halides was investigated. C-N bond formation was achieved in moderate to excellent yields and the catalyst could be separated by magnetic decantation.
- Rafiee, Ezzat,Ataei, Ali,Joshaghani, Mohammad
-
p. 219 - 222
(2015/12/31)
-
- Copper-catalyzed electrophilic amination of organolithiums mediated by recoverable siloxane transfer agents
-
The development and validation of copper-catalyzed, electrophilic amination of aryl and heteroaryl organolithiums with N,N-dialkyl-O-benzoylhydroxylamines have been achieved exploiting recoverable siloxane transfer agents. Given the ready availability of organolithium compounds, the mild reaction conditions, the ease of product purification, and the ready recovery of the siloxane transfer agents, this transformation comprises a useful tactic to access diverse aryl and heteroaryl amines.
- Nguyen, Minh H.,Smith, Amos B.
-
supporting information
p. 4872 - 4875
(2013/10/08)
-
- Porous chitosan microspheres supported-palladium catalyst for the C-N cross-coupling of aryl halides with secondary amines
-
Porous chitosan microspheres-supported palladium catalysed the amination of aryl halides with a wide variety of secondary amines to yield the corresponding cross-coupling products under aerobic conditions. Both aryl bromides and iodides gave good to excellent yields of N,N-disubstituted anilines. The procedure can tolerate common functional groups such as chloro, methoxyl and nitro. The heterogeneous catalysis is efficienct and the catalyst could be recycled seven times without obvious decreased conversion.
- Cheng, Kai,Zeng, Minfeng,Qi, Chenze
-
-
- An efficient palladium-NHC (NHC=N-heterocyclic carbene) and aryl amination pre-catalyst: [Pd(IPr*)(cinnamyl)Cl]
-
The well-defined [Pd(IPr*)(cinnamyl)Cl] complex is reported as one of the best N-heterocyclic carbene (NHC)-based pre-catalysts for the Buchwald-Hartwig amination reaction. This catalytic system displays high efficiency for the coupling of numerous (heter
- Chartoire, Anthony,Frogneux, Xavier,Nolan, Steven P.
-
experimental part
p. 1897 - 1901
(2012/09/25)
-
- A novel and efficient PEPPSI precatalyst
-
The preparation of the novel, well-defined [Pd(IPr*)(3-Cl-pyridinyl) Cl2] complex is described. The steric parameters of the ligand as well as its reactivity in the Buchwald-Hartwig amination were directly compared to other [Pd(NHC)(3-Cl-pyridi
- Chartoire, Anthony,Frogneux, Xavier,Boreux, Arnaud,Slawin, Alexandra M. Z.,Nolan, Steven P.
-
p. 6947 - 6951
(2012/11/14)
-
- Efficient catalytic aryl amination of bromoarenes using 3-iminophosphine palladium(II) chloride
-
While pursuing the development of new hydroamination catalysts, a 3-iminophosphine palladium(II) chloride complex [(3IP)PdCl2] was synthesized that has subsequently proven to be an effective precatalyst for the aryl amination of bromoarenes. This (3IP)PdCl2 complex has been utilized in the catalytic aryl amination of both bromobenzene and bromopyridine derivatives, specifically yielding excellent activity in coupling reactions involving bromobenzene, 4-bromotoluene, and 2-bromopyridine. Using a standard set of catalytic conditions, many alkyl and aryl amines have been investigated as coupling partners in the aryl amination of bromoarenes. In general, secondary alkyl amines and ortho-substituted anilines proved to be the best substrates for this reaction, commonly giving quantitative conversion to products, while primary amines and other anilines gave only poor to moderate results. Catalytic screening data, product yields, and full characterization of isolated products are included.
- Samblanet, Danielle C.,Schmidt, Joseph A. R.
-
p. 7 - 18,12
(2012/12/12)
-
- Highly active well-defined palladium precatalysts for the efficient amination of aryl chlorides
-
The efficient preparation of [Pd(Amphos)(cinnamyl)Cl)] and [Pd(Amphos)(TFA)(κ2-N,C-C6H4-CH 2NMe2)] (Amphos = 4-(di-tert-butylphosphino)-N,N- dimethylaniline and TFA = trifluoroacetate), two new well-defined palladium precatalysts, is reported. These complexes prove highly active in the Buchwald-Hartwig amination reaction, allowing the coupling of a wide range of (hetero)aryl chlorides, including unactivated, neutral, and sterically hindered substrates, with a wide range of amines, including primary and secondary amines. Finally, the catalytic systems have proven efficient at low catalyst loadings ranging from 0.1 to 0.3 mol %.
- Chartoire, Anthony,Lesieur, Mathieu,Slawin, Alexandra M. Z.,Nolan, Steven P.,Cazin, Catherine S. J.
-
experimental part
p. 4432 - 4436
(2011/10/10)
-
- Platinum-catalyzed michael addition and cyclization of tertiary amines with nitroolefins by dehydrogenation of α,β-sp3 C-H bonds
-
A mild platinum-catalyzed oxidative dehydrogenation of α,β- C(sp3)-H bonds of tertiary amines in the presence of ambient oxygen is revealed, and the in situ formed enamines subsequently reacting with various nitroolefins resulted in the development of two one-pot synthetic protocols involving Michael addition-elimination and Michael addition-cyclization. By using different functionalized nitroolefins compatible with the current oxidative conditions, two types of structurally divergent products, trisubstituted enamines and chromano[2,3-b]piperidines, could be expediently accessed, respectively.
- Xia, Xiao-Feng,Shu, Xing-Zhong,Ji, Ke-Gong,Yang, Yan-Fang,Shaukat, Ali,Liu, Xue-Yuan,Liang, Yong-Min
-
supporting information; experimental part
p. 2893 - 2902
(2010/07/09)
-
- Selective functionalization of sp3 C - H bonds adjacent to nitrogen using (diacetoxyiodo)benzene (DIB)
-
(Chemical Equation Presented) A PhI(OAc)2 mediated selective functionalization of sp3C - H bonds adjacent to a nitrogen atom has been reported. When piperidine derivates were used, direct diacetoxylation of α and β sp3 C - H adjacent to a nitrogen atom were observed to afford various cis-2,3-diacetoxylated piperidines. On the other hand, tetrahydroisoquinoline derivatives gave various α-C - H functionalized products in the presence of PhI(OAc)2. Nitroalkanes, dialkyl malonates, and β-keto ester are active participants in this coupling reaction. Meanwhile, α-amino nitriles can also be obtained by oxidative coupling of amineswithmalononitrile. 2009 American Chemical Society.
- Shu, Xing-Zhong,Xia, Xiao-Feng,Yang, Yan-Fang,Ji, Ke-Gong,Liu, Xue-Yuan,Liang, Yong-Min
-
supporting information; experimental part
p. 7464 - 7469
(2010/01/06)
-
- Nickel-catalyzed amination of aryl tosylates
-
(Chemical Equation Presented) The cross-coupling of aryl tosylates with amines and anilines was accomplished by using a Ni-based catalyst system from the combination of Ni(II)-(σ-aryl) complexes/N-heterocyclic carbenes (NHCs). The feature, scope, and limitation of this reaction are disclosed.
- Gao, Cai-Yan,Yang, Lian-Ming
-
p. 1624 - 1627
(2008/09/17)
-
- Modified (NHC)Pd(allyl)Cl (NHC = N-heterocyclic carbene) complexes for room-temperature Suzuki-Miyaura and Buchwald-Hartwig reactions
-
A series of (NHC)Pd(R-allyl)Cl complexes [NHC: IPr = N,N′-bis(2,6- diisopropylphenyl)imidazol-2-ylidene, SIPr = N,N′-bis(2,6- diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene; R = H, Me, gem-Me2, Ph] have been synthesized and fully characterized. When compared to (NHC)Pd(allyl)Cl, substitution at the terminal position of the allyl scaffold favors a more facile activation step. This translates into higher catalytic activity in the Suzuki-Miyaura and Buchwald-Hartwig reactions, allowing for the coupling of unactivated aryl chlorides at room temperature in minutes. In the Suzuki-Miyaura reaction, aryl triflates, bromides, and chlorides react with boronic acids using very low catalyst loading. In the N-aryl amination reaction, a wide range of substrates has been coupled efficiently; primary-, secondary-, alkyl-, or aryl-amines react in high yields with unactivated, neutral, and activated aryl chlorides and bromides. In both reactions, extremely hindered substrates such as tri-ortho-substituted biaryls and tetra-ortho-substituted diarylamines can be produced without loss of activity. Finally, the present catalytic system has proven to be efficient with as low as 10 parts-per-million (ppm) of precatalyst in the Buchwald-Hartwig reaction and 50 ppm in the Suzuki-Miyaura reaction.
- Marion, Nicolas,Navarro, Oscar,Mei, Jianguo,Stevens, Edwin D.,Scott, Natalie M.,Nolan, Steven P.
-
p. 4101 - 4111
(2007/10/03)
-
- Copper-catalyzed N-arylation of amines/amides in poly(ethylene glycol) as recyclable solvent medium
-
The Buchwald N-arylation of amines and amides is achieved efficiently in PEG (400 Daltons) as solvent medium. The solvent and catalyst recyclability is studied. Interestingly amides underwent N-arylation with better yields. Georg Thieme Verlag Stuttgart.
- Chandrasekhar, Srivari,Sultana, S. Shameem,Yaragorla, Srinivasa Rao,Reddy, N. Ramakrishna
-
p. 839 - 842
(2007/10/03)
-
- Scope and utility of CsOH·H2O in animation reactions via direct coupling of aryl halides and sec-alcyclic amines
-
Direct coupling of aryl halides with sec-alicyclic amines promoted by CsOH·H2O in DMSO to the corresponding aryl substituted amines, with good to excellent yields, is reported herein. A variety of aryl halides and sec-alicyclic amines with a broad range of electronic diversity and functional groups was studied in this transformation, thus offering general applicability in organic synthesis.
- Varala, Ravi,Ramu,Alam, M. Mujahid,Adapa, Srinivas R.
-
p. 1747 - 1750
(2007/10/03)
-
- Palladium-catalyzed microwave-assisted amination of 1-bromonaphthalenes and 5-and 8-bromoquinolines
-
1-Aminonaphthalenes and 5-and 8-aminoquinolines were rapidly prepared from the respective aryl bromides in good yields by Pd-catalyzed aryl amination under microwave conditions. Consistent improvements in yields over those obtained under standard conditions were seen with quinoline substrates. In the cases where 5-bromo-8-cyanoquinoline was used as a substrate, no desired products were obtained under standard conditions with a number of different primary and secondary amines. However, microwave conditions provided the desired products in good to excellent yields.
- Wang, Tammy,Magnin, David R.,Hamann, Lawrence G.
-
p. 897 - 900
(2007/10/03)
-
- Highly Selective Aromatic Chlorination. Part 4. The Chlorination of Aromatic Hydrocarbons with N-Chloroamines in Acidic Solution
-
Benzene, toluene, some polymethylbenzenes, and naphthalene have been treated with N-chlorotrialkylammonium salts and N-chlorodialkylamines in trifluoroacetic acid at room temperature.With benzene, toluene, and 1,3,5-trimethylbenzene the major products arise from aromatic chlorination whereas with the other polymethylbenzenes side-chain reactions predominate.By controlling the acidity of the reaction and the nature of the N-chloroamine, the chlorination of toluene can be made to give preferentially 2- or 4-chlorination.However, the selectivities are not as great as reported previously with electron-rich aromatic compounds with a ?-donor substituent.The products from the reaction of naphthalene are very dependent on the structure of the N-chlorinated amine.The bulky N-chlorotrialkylammonium salts selectively chlorinate the 1-position, but in low yield, whereas the less hindered N-chloropiperidine gives good yields of 1-(1-piperidino)-naphthalene.The results from these studies are discussed in terms of arenium-ion and electron-transfer mechanisms.
- Smith, John R. Lindsay,McKeer, Linda C.,Taylor, Jonathan M.
-
p. 1537 - 1544
(2007/10/02)
-