29778-20-9Relevant articles and documents
Highly efficient synthesis of 1,2-disubstituted acetylenes derivatives from the cross-coupling reactions of 1-bromoalkynes with organotitanium reagents
Li, Qing-Han,Wu, Chuan
supporting information, (2021/08/25)
A Highly efficient route for the synthesis of 1,2-disubstituted acetylene derivatives has been developed by nickel catalyzed cross-couplings of alkynyl halides with aryl titanium reagents under mild conditions. This has given corresponding cross-coupling products good to excellent isolated yields of up to 92 %. The aryls bearing electron-donating or electron-withdrawing groups in either alkynylhalides or aryltitanium substrates gave cross-coupling products good yields. This process was simple and easily performed, which provides an efficient method for the synthesis of 1,2-disubstituted acetylenes derivatives.
Ligand-Promoted Alkynylation of Aryl Ketones: A Practical Tool for Structural Diversity in Drugs and Natural Products
Xu, Hui,Ma, Biao,Fu, Zunyun,Li, Han-Yuan,Wang, Xing,Wang, Zhen-Yu,Li, Ling-Jun,Cheng, Tai-Jin,Zheng, Mingyue,Dai, Hui-Xiong
, p. 1758 - 1764 (2021/02/09)
Conversion of the numerous aryl ketones into aryl electrophiles via Ar-C(O) cleavage remains a challenging yet highly desirable transformation in Sonogashira-type coupling. Herein, we report a palladium-catalyzed ligand-promoted alkynylation of unstrained aryl ketones. The protocol allows the alkynylation to be carried out in a one-pot procedure with broad functional-group tolerance and substrate scope. The potential applications of this protocol in drug discovery and chemical biology are further demonstrated by late-stage diversification of a number of pharmaceuticals and natural products. More importantly, two different biologically important fragments derived from a pharmaceutical and natural product could be connected by the consecutive alkynylation of ketones. Distinct from aryl halides in conventional Sonogashira reactions, the protocol provides a practical tool for the 1,2-bifunctionalization of aryl ketone by merging ketone-directed ortho-C-H activation with ligand-promoted ipso-Ar-C(O) alkynylation.
Cobalt catalyzed stereodivergent semi-hydrogenation of alkynes using H2O as the hydrogen source
Li, Kangkui,Khan, Ruhima,Zhang, Xuexin,Gao, Yang,Zhou, Yongyun,Tan, Heng,Chen, Jingchao,Fan, Baomin
supporting information, p. 5663 - 5666 (2019/05/21)
Cobalt-catalyzed stereodivergent semi-hydrogenation of internal alkynes to alkenes is developed. The reaction proceeded through transfer hydrogenation under mild conditions using a base metal CoI2 as the catalyst, and H2O/MeOH as the hydrogen source with Zn as the reductant. The E/Z-selectivity of the product could be switched by changing the solvent and by inclusion/exclusion of a bidentate phosphine ligand (dppe). This method provides a simple and cost effective pathway for the synthesis of 1,2-dideuterioalkenes.
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
supporting information, 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.
A palladium catalyzed aryl alkyne preparation method
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Paragraph 0037; 0038; 0039, (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.
Highly efficient synthesis of 1,2-disubstituted acetylenes derivatives from the cross-coupling reactions of 1-bromoalkynes with organoalane reagents
Shao, Xue-Bei,Jiang, Xin,Li, Qing-Han,Zhao, Zhi-Gang
, p. 6063 - 6070 (2018/09/12)
A Highly efficient route for the synthesis of 1,2-disubstituted acetylene derivatives has been developed by palladium catalyzed cross-couplings of alkynyl halides with (hetero)aryl aluminium reagents under mild conditions. This has given corresponding cross-coupling products good to excellent isolated yields of up to 99%. The aryls bearing electron-donating or electron-withdrawing groups in either alkynylhalides or arylaluminum substrates gave cross-coupling products good yields. This process was simple and easily performed, which provides an efficient method for the synthesis of 1,2-disubstituted acetylenes derivatives. On the basis of the experimental results, a possible catalytic cycle has been proposed.
Recyclable heterogeneous metal foil-catalyzed cyclopropenation of alkynes and diazoacetates under solvent-free mechanochemical reaction conditions
Chen, Longrui,Leslie, Devonna,Coleman, Michael G.,Mack, James
, p. 4650 - 4661 (2018/05/30)
Silver and copper foil were found to be effective, versatile and selective heterogeneous catalysts for the cyclopropenation of terminal and internal alkynes under mechanochemical reaction conditions. This methodology enables the functionalization of a wide range of terminal or internal alkynes under ambient, aerobic, and solvent-free conditions. Finally, we have demonstrated a unique and versatile one-pot domino Sonogashira-cyclopropenation mechanochemical reaction for the formation of complex cyclopropenes.
Visible-Light-Assisted Cobalt-2-(hydroxyimino)-1-phenylpropan-1-one Complex Catalyzed Pd/Cu-Free Sonogashira–Hagihara Cross-Coupling Reaction
Song, Jin-Yi,Zhou, Xuan,Song, He,Liu, Yang,Zhao, Hong-Yan,Sun, Zhi-Zhong,Chu, Wen-Yi
, p. 758 - 762 (2018/01/27)
An effective and inexpensive strategy for the Co(C9H9NO2)3 catalyzed Sonogashira–Hagihara cross-coupling reaction of aryl bromides containing electron-rich and electron-poor substituents with terminal alkynes wa
Sonogashira-type cross-coupling reactions catalyzed by copper complexes of pincer N-heterocyclic carbenes
Domyati, Doaa,Latifi, Reza,Tahsini, Laleh
supporting information, p. 98 - 105 (2018/03/06)
Copper complexes of N-heterocyclic carbenes (NHC) have recently received great attention in catalysis, however, the application scope has been limited to neutral complexes bearing monodentate ligands. Herein, we report the synthesis and full characterization of a cationic Cu-pincer bis(NHC) complex with bulky tert-butyl wingtips that serves as catalyst for the coupling of aryl iodides and phenylacetylene, alongside its analogs with small alkyl substituents. Unlike other copper catalysts that require an inert atmosphere to prevent alkyne homocoupling, a competing side reaction to Sonogashira reaction, the Cu-pincer bis(NHC) complexes provide good to excellent cross-coupling yields in air. Interestingly, the reaction under argon affords substantially reduced cross-coupling, indicative of the oxygen involvement and its facilitating effect in the mechanism. In our controlled studies, the air-assisted cross-coupling reaction came to a complete stop when using a radical trap, suggesting the presence of a radical in the mechanism. Examining the reaction of Cu-pincer bis(NHC) complexes with oxygen via UV–vis spectroscopy reveals a dark green chromophore formation at ?40 °C with strong absorbance (ε > 400 M?1cm?1) at 460 nm and 500 nm, likely due to a high-valent copper-oxygen adduct.
Method for synergistically catalyzing Sonogashira cross-coupling reaction with carbonyl iron cluster compounds and trace palladium
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Paragraph 0024; 0025; 0026; 0027; 0028-0047; 0052; 0053, (2017/07/19)
The invention discloses a method for synergistically catalyzing a Sonogashira cross-coupling reaction with carbonyl iron cluster compounds and trace palladium. According to the method, palladium chloride and triiron dodecarbonyl are taken as catalysts, acetylenic ketone is taken as a ligand, methanol is taken as a solvent, aryl halide, terminal alkyne and K2CO3 are subjected to a reaction , and arylethynylene compounds are obtained. With the adoption of the method, the use amount of palladium metal is reduced obviously, reaction operation is simple, the condition is mild (the temperature is commonly about 60 DEG C), compatibility of functional groups is good, the yield is high, the use quantity of the catalysts is low, and the productivity is high.
