4783-78-2Relevant academic research and scientific papers
Ligand compound for copper catalyzed aryl halide coupling reaction, catalytic system and coupling reaction
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Paragraph 0134-0138; 0140, (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.
Ni-Catalyzed Aryl Sulfide Synthesis through an Aryl Exchange Reaction
Isshiki, Ryota,Kurosawa, Miki B.,Muto, Kei,Yamaguchi, Junichiro
supporting information, p. 10333 - 10340 (2021/07/21)
A Ni-catalyzed aryl sulfide synthesis through an aryl exchange reaction between aryl sulfides and a variety of aryl electrophiles was developed. By using 2-pyridyl sulfide as a sulfide donor, this reaction achieved the synthesis of aryl sulfides without using odorous and toxic thiols. The use of a Ni/dcypt catalyst capable of cleaving and forming aryl-S bonds was important for the aryl exchange reaction between 2-pyridyl sulfides and aryl electrophiles, which include aromatic esters, arenol derivatives, and aryl halides. Mechanistic studies revealed that Ni/dcypt can simultaneously undergo oxidative additions of aryl sulfides and aromatic esters, followed by ligand exchange between the generated aryl-Ni-SR and aryl-Ni-OAr species to furnish aryl exchanged compounds.
Mechanochemical Solvent-Free Catalytic C?H Methylation
Ni, Shengjun,Hribersek, Matic,Baddigam, Swarna K.,Ingner, Fredric J. L.,Orthaber, Andreas,Gates, Paul J.,Pilarski, Lukasz T.
supporting information, p. 6660 - 6666 (2020/12/18)
The mechanochemical, solvent-free, highly regioselective, rhodium-catalyzed C?H methylation of (hetero)arenes is reported. The reaction shows excellent functional-group compatibility and is demonstrated to work for the late-stage C?H methylation of biologically active compounds. The method requires no external heating and benefits from considerably shorter reaction times than previous solution-based C?H methylation protocols. Additionally, the mechanochemical approach is shown to enable the efficient synthesis of organometallic complexes that are difficult to generate conventionally.
N - And O -arylation of pyridin-2-ones with diaryliodonium salts: Base-dependent orthogonal selectivity under metal-free conditions
Abe, Yusuke,Hanazawa, Natsumi,Katagiri, Kotone,Kuriyama, Masami,Ono, Shimpei,Onomura, Osamu,Yamamoto, Kosuke
, p. 8295 - 8300 (2020/09/09)
Metal-free N- and O-arylation reactions of pyridin-2-ones as ambident nucleophiles have been achieved with diaryliodonium salts on the basis of base-dependent chemoselectivity. In the presence of N,N-diethylaniline in fluorobenzene, pyridin-2-ones were very selectively converted to N-arylated products in high yields. On the other hand, the O-arylation reactions smoothly proceeded with the use of quinoline in chlorobenzene, leading to high yields and selectivities. In these methods, a variety of pyridin-2-ones in addition to pyridin-4-one and a set of diaryliodonium salts were accepted as suitable reaction partners.
Benzylic C?H Functionalisation by [Et3SiH+KOtBu] leads to Radical Rearrangements in o-tolyl Aryl Ethers, Amines and Sulfides
Arokianathar, Jude N.,Kolodziejczak, Krystian,Bugden, Frances E.,Clark, Kenneth F.,Tuttle, Tell,Murphy, John A.
supporting information, p. 2260 - 2267 (2020/05/06)
Reaction of Et3SiH+KOtBu with diaryl ethers, sulfides and amines that feature an ortho alkyl group leads to rearrangement products. The rearrangements arise from formation of benzyl radicals, likely formed through hydrogen atom abstraction by triethylsilyl radicals. The rearrangements involve cyclisation of the benzyl radical onto the partner arene, which, from computation, is the rate determining step. In the case of diaryl ethers, Truce-Smiles rearrangements arise from radical cyclisations to form 5-membered rings, but for diarylamines, cyclisations to form dihydroacridines are observed. (Figure presented.).
A directing group-assisted ruthenium-catalyzed approach to access: Meta -nitrated phenols
Sasmal, Sheuli,Sinha, Soumya Kumar,Lahiri, Goutam Kumar,Maiti, Debabrata
supporting information, p. 7100 - 7103 (2020/07/14)
meta-Selective C-H nitration of phenol derivatives was developed using a Ru-catalyzed σ-activation strategy. Cu(NO3)2·3H2O was employed as the nitrating source, whereas Ru3(CO)12 was found to be the most suitable metal catalyst for the protocol. Mechanistic studies suggested involvement of an ortho-CAr-H metal intermediate, which promoted meta-electrophilic aromatic substitution and silver-assisted free-radical pathway.
Identification of an Oxalamide Ligand for Copper-Catalyzed C?O Couplings from a Pharmaceutical Compound Library
Chan, Vincent S.,Krabbe, Scott W.,Li, Changfeng,Sun, Lijie,Liu, Yue,Nett, Alex J.
, (2019/04/30)
A typical pharmaceutical compound library is stocked with molecular diversity and could provide a platform for the discovery of new ligand structures. Herein, we describe the use of this approach in combination with high throughput screening to identify N,N’-bis(thiophene-2-ylmethyl)oxalamide as a ligand that is generally effective for copper-catalyzed C?O cross-couplings to prepare both biarylethers as well as phenols under mild conditions.
Transition-Metal-Catalyzed Transformation of Sulfonates via S-O Bond Cleavage: Synthesis of Alkyl Aryl Ether and Diaryl Ether
Chen, Xuemeng,Xiao, Xue,Sun, Haotian,Li, Yue,Cao, Haolin,Zhang, Xuemei,Yang, Shengyong,Lian, Zhong
supporting information, p. 8879 - 8883 (2019/11/14)
The catalytic conversion of sulfonates, a versatile class of pharmaceutical intermediates, is usually based on C-O bond cleavage. In this paper, however, we discover a rare transformation of sulfonates via S-O bond cleavage catalyzed by transition metal, through which alkyl sulfonates could undergo an intramolecular desulfitative C-O coupling to form aryl alkyl ethers in the presence of a nickel catalyst. Meanwhile, aryl sulfonates perform similarly to give diaryl ethers catalyzed by a palladium complex. This transformation could tolerate a wide range of functionalities. Controlled experiments reveal that the 2-pyridyl group is necessary to promote the reaction as designed. Crossover experiments proved that this transformation might proceed partly in an intermolecular pathway.
Substituent Effects of 2-Pyridones on Selective O-Arylation with Diaryliodonium Salts: Synthesis of 2-Aryloxypyridines under Transition-Metal-Free Conditions
Li, Xiao-Hua,Ye, Ai-Hui,Liang, Cui,Mo, Dong-Liang
, p. 1699 - 1710 (2018/02/06)
An efficient transition-metal-free strategy to synthesize 2-aryloxypyridine derivatives has been developed by a selective O-arylation of 2-pyridones with diaryliodonium salts. The reaction was compatible with a series of functional groups for 2-pyridones and diaryliodonium salts such as halides, nitro, cyano, and ester groups. The substituents at the C6-position of 2-pyridones favored O-arylation products because of steric hindrance. The reaction was easily performed on a gram-scale and 6-chloro-2-pyridone was a good precursor to access various unsubstituted 2-aryloxypyridines by dehalogenation. A P2Y 1 lead compound analogue could be prepared in good yield over two steps.
A ortho-nitro phenol and its derivative synthesis method (by machine translation)
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Paragraph 0092, (2017/08/23)
The invention relates to a method for the synthesis of organic compounds, in the existing technology of O-nitrophenol strong acid used in the synthesis process of the serious problem of environmental pollution and the synthesis step longer more complicated problem, the invention provides a ortho-nitro phenol and synthetic method of derivative thereof, proceeding by the phenol compound, synthesis of 2 - (phenoxy) pyridine, the obtained product, catalyst, tert-butyl nitrite, organic solvent and adding sealing in the pressure containers, in oil bath heating 50 - 100 °C, reaction 10 - 30 hours, to obtain 2 - (2 - nitrobenzene) ethoxy pyridine; re-processing by the ortho-nitro phenol and its derivatives; the method is simple, high-efficiency. (by machine translation)
