29778-28-7Relevant academic research and scientific papers
A facile protocol for copper-free palladium-catalyzed Sonogashira coupling in aqueous media
Jung, Da-Young,Park, Soo Youl,Kim, Seung-Hoi
supporting information, p. 110 - 116 (2021/11/09)
The combination of a readily available palladium catalyst and an eco-friendly basic aqueous solution of room-temperature ionic liquid, choline hydroxide (ChOH), was used in a facile protocol alternative to the Sonogashira coupling reaction, alkynylation of aryl halides in the absence of a copper cocatalyst and an external base. The dual nature of ChOH to act as a base and a green solvent played a crucial role in the catalytic cycle. The coupling reaction progressed efficiently to form a Csp-Csp2 bond under the identified conditions although the reaction outcome depended significantly on the substrates.
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.
Facile one-pot synthesis of diarylacetylenes from arylaldehydes: Via an addition-double elimination process
Chen, Jianyang,Zhang, Xuan,Wu, Jiajun,Wang, Rui,Lei, Chunlin,An, Yanan
, p. 4701 - 4705 (2021/06/11)
A practical one-pot protocol has been developed to synthesize diarylacetylenes from arylaldehydes by treatment with 1-(arylmethyl)benzotriazoles and LiN(SiMe3)2. The reaction proceeded through imine formation, Mannich-type addition and double elimination to deliver products in up to 99% yields with broad substrate scope. In addition, gram-scale synthesis of 1-bromo-4-(phenylethynyl)benzene has been demonstrated.
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.
Simple and efficient diaryl alkyne synthesis method
-
Paragraph 0026; 0029-0031, (2021/04/14)
The embodiment of the invention discloses a simple and efficient diaryl alkyne synthesis method. The method comprises the steps of by taking arylmethylbenzotriazole and aromatic aldehyde as raw materials, carrying out addition and double-beta-elimination reaction under the action of bis (trimethylsilyl) amino salt MN (SiMe3) 2 to synthesize diaryl alkyne by a one-pot method. The raw materials and chemical reagents used in the method are easy to obtain, the reaction conditions are mild, the operation is simple, the substrate universality is good, the product yield is high, and the method is a simple and efficient diaryl alkyne synthesis method.
Sodium-metal-promoted reductive 1,2-syn-diboration of alkynes with reduction-resistant trimethoxyborane
Fukazawa, Mizuki,Ito, Shiori,Nogi, Keisuke,Takahashi, Fumiya,Yorimitsu, Hideki
, p. 1171 - 1179 (2020/10/18)
Reductive 1,2-diboration of alkynes has been accomplished by means of sodium dispersion in the presence of trimethoxyborane as a reduction-resistant boron electrophile. Two boron moieties can be introduced onto alkynes with excellent syn selectivity to afford the corresponding (Z)-1,2-diborylalkenes. Bis(borate) species generated in situ can be involved in one-pot Suzuki-Miyaura arylation, formal arylboration of alkynes thus being executed.
Copper-Catalyzed Oxidative Cross-Coupling of Electron-Deficient Polyfluorophenylboronate Esters with Terminal Alkynes
Liu, Zhiqiang,Budiman, Yudha P.,Tian, Ya-Ming,Friedrich, Alexandra,Huang, Mingming,Westcott, Stephen A.,Radius, Udo,Marder, Todd B.
supporting information, p. 17267 - 17274 (2020/12/01)
We report herein a mild procedure for the copper-catalyzed oxidative cross-coupling of electron-deficient polyfluorophenylboronate esters with terminal alkynes. This method displays good functional group tolerance and broad substrate scope, generating cro
Sequentially Pd/Cu-Catalyzed Alkynylation-Oxidation Synthesis of 1,2-Diketones and Consecutive One-Pot Generation of Quinoxalines
Niesobski, Patrik,Martínez, Ivette Santana,Kustosz, Sebastian,Müller, Thomas J. J.
supporting information, p. 5214 - 5218 (2019/07/31)
We report a simple and efficient one-pot synthesis of 1,2-diketones by concatenation of two Pd/Cu-catalyzed processes: Pd0/CuI-catalyzed Sonogashira coupling of terminal alkynes with aryl (pseudo)halides furnishes internal alkynes, which are directly transformed by PdII/CuII-catalyzed Wacker-type oxidation with DMSO and oxygen as dual oxidants to furnish 1,2-diketones. With this efficient, catalyst economical process, various aryl iodides and triflates are efficiently transformed in high yields into symmetrically and unsymmetrically substituted 1,2-diketones with various functional groups. This process can be readily extended to a consecutive one-pot synthesis of quinoxalines in a diversity-oriented fashion.
Copper-Catalyzed Twofold Silylmetalation of Alkynes
Shimokawa, Jun,Yamagishi, Hiroki,Yorimitsu, Hideki
supporting information, p. 1551 - 1554 (2019/08/07)
The first twofold silylmetalation across a C≡C triple bond was achieved. In the presence of a catalytic amount of copper cyanide, diarylacetylenes were converted into 1,2-dimetalated 1,2-disilyl-1,2-diarylethanes on treatment with silylpotassium species generated in situ from disilane and t -BuOK. The dimetalated species were subsequently protonated to yield a series of 1,2-disilyl-1,2-diarylethanes.
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.
