35684-12-9Relevant articles and documents
Cu2O Nanocrystals-Catalyzed Photoredox Sonogashira Coupling of Terminal Alkynes and Arylhalides Enhanced by CO2
Shanmugam, Munusamy,Sagadevan, Arunachalam,Charpe, Vaibhav Pramod,Pampana, V. Kishore Kumar,Hwang, Kuo Chu
, p. 287 - 292 (2019/11/05)
Herein the first visible-light-activated Sonogashira C?C coupling reaction at room temperature catalyzed by single-metal heterogeneous Cu2O truncated nanocubes (Cu2O TNCs) was developed. A wide variety of aryl halides and terminal alkynes worked well in this recyclable heterogeneous photochemical process to form the corresponding Sonogashira C?C coupling products in good yields. Mechanistic control studies indicated that CO2 enhances the formation of light-absorbing heterogeneous surface-bound CuI-phenylacetylide (λmax=472 nm), which further undergoes single-electron transfer with aryl iodides/bromides to enable Sonogashira Csp2 ?Csp bond formation. In contrast to literature-reported bimetallic TiO2-containing nanoparticles as photocatalyst, this work avoided the need of cocatalysis by TiO2. Single-metal CuI in Cu2O TNCs was solely responsible for the observed Csp2 ?Csp coupling reactions under CO2 atmosphere.
Method for preparing aryl internal alkyne compound through light-mediated copper catalysis
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Paragraph 0031-0033; 0037-0039, (2020/09/09)
The invention relates to a method for preparing an aryl internal alkyne compound through light-mediated copper catalysis, and belongs to the field of organic chemistry. An aryl sulfide salt and a terminal alkyne are used as raw materials, a + 1 valent copper salt is used as a catalyst, potassium carbonate is used as alkali, reaction is performed in solvents such as DMSO to obtain the aryl internalalkyne compound, and the yield is 50%-86%. According to the synthetic method, the raw materials are easy to obtain, the reaction conditions are mild, a simple, convenient, green and efficient synthetic route of the internal alkyne compound is provided, and an effective method for introducing alkynyl into aromatic ring-containing drug molecules is provided.
Pd-Catalyzed decarboxylative alkynylation of alkynyl carboxylic acids with arylsulfonyl hydrazides via a desulfinative process
Chang, Sheng,Liu, Ying,Yin, Shu Zhu,Dong, Lin Lin,Wang, Jian Feng
, p. 5357 - 5362 (2019/04/04)
In the presence of a Pd(ii)/P-ligand catalytic system, decarboxylative alkynylation of alkynyl carboxylic acids and arylsulfonyl hydrazides by desulfinative coupling could provide aryl alkynes in satisfactory yields by either judiciously selecting palladium catalysts or modulating phosphine ligands under mild conditions. The reported coupling reactions are very practical as they do not require the protection of inert gas or oxygen and are tolerant to many functional groups.
Pd-catalyzed Sonogashira coupling in aqueous media. Observation of micelles that contain substrates and catalyst
Suzaki, Yuji,Kobayashi, Yuka,Tsuchido, Yoshitaka,Osakada, Kohtaro
, p. 106 - 111 (2019/01/23)
Sonogashira-coupling of 4-iodoanisole with 4-methylphenylacetylene was conducted in the presence of Pd(II) catalyst, NEt3, CuI and sodium dodecylsulfonate (SDS) in aqueous media. The reaction catalyzed by PdCl2(Me2NCH2CH2NMe2) (2b) at 80 °C affords 4-methoxyphenyl-4′-methylphenylalkyne in 51% yield after 2.0 h, whereas those catalyzed by the complexes with other ethylenediamine derivatives, PdCl2(R2NCH2CH2NR2) (R[dbnd]H, C2H5, C3H7, C4H9, and C6H13), formed the product in lower yields (18–26%). Aqueous solution of complex 2b (5.3 mM) and SDS (168 mM) forms a yellow colloidal solution, which is stable for one night at room temperature. The complexes of ethylenediamines with higher alkyl substituents on the nitrogen atoms do not form apparently homogeneous solutions. TEM (transmission electron micrograph) observation of the former solution ([2b] = 5.3 mM), layered on a copper grid surface, revealed formation of Pd-containing micelles with diameters of ca. 4.0–6.0 nm A mixture of 2b (5.4 mM), 4-iodoanisole (125 mM) and 4-methylphenyl acetylene (250 mM) in water contains micelles with diameters smaller than 40 nm, as is clearly observed by TEM. Mixtures of the other complexes and the substrates contain micelles with larger sizes, and their TEM images are obscure. Thus, complex 2b forms small and clear micelles containing the catalyst and the substrate in the reaction mixture, and the micelle formation enhances the reaction in aqueous media.
A palladium catalyzed aryl alkyne preparation method
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Paragraph 0034; 0035; 0036, (2019/05/21)
The invention discloses a palladium catalyzed aryl alkyne of the preparation method, comprises the following steps: in the catalyst, under the action of the ligand and alkali, substituted with aryl sulfonyl chloride alkynoic occurs in the organic solvent escapes suosuo the coupling reaction, after the reaction is finished after treatment to obtain the aryl alkyne. Used in the preparation method of the cheap raw material, the reaction and simple post treatment operation, at the same time, the reaction less side reaction, high yield of the product.
Functionalized α,β-ynones: Efficient ligand for Cu catalyzed Sonogashira-type cross-coupling reaction
Wang, Xian,Wang, Zhenhua,Xie, Zunyuan,Zhang, Guofang,Zhang, Weiqiang,Gao, Ziwei
, p. 109296 - 109300 (2016/11/30)
Under the classic reaction conditions, a large excess of copper catalyst and N, O donor ligands were mandatory for the catalytic cross-coupling of Csp2-Csp bonds. Herein, we wish to report α,β-ynones as σ-, π-electron donating ligands for copper catalyzed Sonogashira-type reaction. As low as 0.25-2.5 mol% of L11 (3-(4-bromophenyl)-1-(4-methoxyphenyl)prop-2-yn-1-one) significantly accelerated the 0.1-1.0 mol% of CuI catalyzed cross-coupling of aryl iodides with terminal alkynes and alkynylcarboxylic acids, respectively. This low-mol% catalyst system showed satisfactory activity and tolerance with 36 examples of substituted alkynes.
Synthesis of diarylalkynes via tandem Sonogashira/decarboxylative reaction of aryl chlorides with propiolic acid
Li, Xiang,Yang, Fan,Wu, Yangjie
, p. 13738 - 13741 (2014/04/03)
A facile and efficient protocol for one-pot synthesis of diarylalkynes via tandem Sonogashira/decarboxylative coupling has been developed. The remarkable features of this reaction include using commercially available aryl chlorides as starting materials and taking the propiolic acid instead of expensive terminal alkynes as an acetylene source. This journal is the Partner Organisations 2014.
