31053-03-9Relevant articles and documents
Substituent effects in the gas-phase pyrolysis of 4-(N/-arylamino)-1-butyl acetate and 5-(N/-arylamino)-1-pentyl acetate
Al-Awadi, Nouria A.,Elnagdi, Mohamed H.,Kaul, Kamini,Chuchani, Gabriel
, p. 675 - 678 (2000)
A kinetic study of the gas-phase pyrolysis of 4- and 5-(N-arylamino)-1-butyl and -1-pentyl acetate was mace. Each ester was pyrolysed at five or six different temperatures and over a temperature range not less than 50 °C. These reactions were homogeneous and unimolecular. The reactivities of these compounds were compared with those of the parent compounds 4- and 5-(N-phenyl)-1-butyl and -1-pentyl acetate and with each other. The products of the decomposition reaction of these compounds suggest an anchimeric assistance of the amino substituen for a trans elimination, indicating that an ion-pair type of mechanism may be operating during the process of elimination. Copyright
Successful application of microstructured continuous reactor in the palladium catalysed aromatic amination
Mauger, Christelle,Buisine, Olivier,Caravieilhes, Sylvain,Mignani, Gérard
, p. 3627 - 3629 (2005)
Micro reactor technology was successfully applied in the palladium catalysed C-N cross-coupling reaction between 4-bromotoluene and piperidine. Excellent conversions and selectivities were obtained without any by-product formation in continuous reactor.
Catalytic Amination of Phenols with Amines
Chen, Kai,Kang, Qi-Kai,Li, Yuntong,Wu, Wen-Qiang,Zhu, Hui,Shi, Hang
supporting information, p. 1144 - 1151 (2022/02/05)
Given the wide prevalence and ready availability of both phenols and amines, aniline synthesis through direct coupling between these starting materials would be extremely attractive. Herein, we describe a rhodium-catalyzed amination of phenols, which provides concise access to diverse anilines, with water as the sole byproduct. The arenophilic rhodium catalyst facilitates the inherently difficult keto–enol tautomerization of phenols by means of π-coordination, allowing for the subsequent dehydrative condensation with amines. We demonstrate the generality of this redox-neutral catalysis by carrying out reactions of a large array of phenols with various electronic properties and a wide variety of primary and secondary amines. Several examples of late-stage functionalization of structurally complex bioactive molecules, including pharmaceuticals, further illustrate the potential broad utility of the method.
Ligand compound for copper catalyzed aryl halide coupling reaction, catalytic system and coupling reaction
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Paragraph 0086-0091; 0098, (2021/05/29)
The invention provides a ligand compound capable of being used for copper catalyzed aryl halide coupling reaction, the ligand compound is a three-class compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group, and the invention also provides a catalytic system for the aryl halide coupling reaction. Thecatalytic system comprises a copper catalyst, a compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group adopted as a ligand, alkali and a solvent, and meanwhile, the invention also provides a system for the aryl halide coupling reaction adopting the catalyst system. The compound containing the 2-(substituted or non-substituted) aminopyridine nitrogen oxygen group can be used as the ligand for the copper catalyzed aryl chloride coupling reaction, and the ligand is stable under a strong alkaline condition and can well maintain catalytic activity when being used for the copper-catalyzed aryl chloride coupling reaction. In addition, the copper catalyst adopting the compound as the ligand can particularly effectively promote coupling of copper catalyzed aryl chloride and various nucleophilic reagents which are difficult to generate under conventional conditions, C-N, C-O and C-S bonds are generated, and numerous useful small molecule compounds are synthesized. Therefore, the aryl halide coupling reaction has a very good large-scale application prospect by adopting the copper catalysis system of the ligand.
Iodine-Mediated Coupling of Cyclic Amines with Sulfonyl Hydrazides: an Efficient Synthesis of Vinyl Sulfone Derivatives
Rong, Xiaona,Guo, Jingwen,Hu, Zheqi,Huang, Lehao,Gu, Yugui,Cai, Yuepiao,Liang, Guang,Xia, Qinqin
supporting information, p. 701 - 708 (2020/12/30)
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.
Metal-free late-stage C(sp2)-H functionalization of: N -aryl amines with various sodium salts
Mudithanapelli, Chandrashekar,Kim, Mi-Hyun
, p. 450 - 464 (2020/02/03)
Metal-free consecutive C(sp2)-X (X = Cl, Br, S, N) bond formations of N-aryl amines (cyclic, fused, carbamate, and aminium radicals) were achieved under mild conditions using [bis(trifluoroacetoxy)iodo]benzene (PIFA) and simple nonharmful sodium salts. This direct and selective C(sp2)-H functionalization showed excellent functional group compatibility, cost effectiveness, and late-stage applicability for the synthesis of biologically active natural products. Two mechanisms were proposed to explain the ortho- or para-preference, as well as the accelerating effect of CH3NO2
Iron-Catalyzed Oxidative C?C Cross-Coupling Reaction of Tertiary Anilines with Hydroxyarenes by Using Air as Sole Oxidant
Purtsas, Alexander,Kataeva, Olga,Kn?lker, Hans-Joachim
, p. 2499 - 2508 (2020/02/11)
A mild procedure for the oxidative C?C cross-coupling of tertiary anilines with phenols is described which provides the products generally in high yields and with excellent selectivity. The reaction is catalyzed by the hexadecafluorinated iron–phthalocyanine complex FePcF16 in the presence of substoichiometric amounts of methanesulfonic acid and ambient air as sole oxidant.
General Paradigm in Photoredox Nickel-Catalyzed Cross-Coupling Allows for Light-Free Access to Reactivity
Nocera, Daniel G.,Qin, Yangzhong,Sun, Rui
supporting information, p. 9527 - 9533 (2020/04/08)
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.
Palladium Complexes Based on Ylide-Functionalized Phosphines (YPhos): Broadly Applicable High-Performance Precatalysts for the Amination of Aryl Halides at Room Temperature
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)
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.
Electron Donor-Acceptor Complex-Initiated Photochemical Cyanation for the Preparation of α-Amino Nitriles
Xia, Qing,Li, Yufei,Cheng, Lan,Liang, Xin,Cao, Chenlin,Dai, Peng,Deng, Hongping,Zhang, Weihua,Wang, Qingmin
supporting information, p. 9638 - 9643 (2020/12/21)
An electron donor-acceptor complex-initiated α-cyanation of tertiary amines has been described. The reaction protocol provides a novel method to synthesize various α-amino nitriles under mild conditions. The reaction can proceed smoothly without the presence of photocatalysts and transition metal catalysts, and either oxidants are unnecessary or O2 is the only oxidant. The practicality of this method is showcased not only by the late-stage functionalization of natural alkaloid derivatives and pharmaceutical intermediate, but also by the applicability of a stop-flow microtubing reactor.
