704-97-2Relevant articles and documents
Cobalt-Mediated Decarboxylative/Desilylative C?H Activation/Annulation Reaction: An Efficient Approach to Natural Alkaloids and New Structural Analogues
Hai, Li,Lai, Ruizhi,Lv, Shan,Nie, Ruifang,Wu, Yong,Yang, Zhongzhen,chen, Kang
, (2022/02/03)
A Co(II)-mediated decarboxylative/desilylative C?H activation/annulation reaction for the efficient synthesis of 3-arylisoquinolines has been developed. Using alkynyl carboxylic acid and alkynyl silane as terminal alkyne precursors, providing straightforw
Organocatalytic Strategy for the Fixation of CO2via Carboxylation of Terminal Alkynes
Shi, Jun-Bin,Bu, Qingqing,Liu, Bin-Yuan,Dai, Bin,Liu, Ning
, p. 1850 - 1860 (2021/01/14)
An organocatalytic strategy for the direct carboxylation of terminal alkynes with CO2 has been developed. The combined use of a bifunctional organocatalyst and Cs2CO3 resulted in a robust catalytic system for the preparation of a range of propiolic acid derivatives in high yields with broad substrate scope using CO2 at atmospheric pressure under mild temperatures (60 °C). This work has demonstrated that this organocatalytic method offers a competitive alternative to metal catalysis for the carboxylation of terminal alkynes and CO2. In addition, this protocol was suitable for the three-component carboxylation of terminal alkynes, alkyl halides, and CO2.
Microwave-assisted fabrication of a mixed-ligand [Cu4(μ3-OH)2]-cluster-based metal–organic framework with coordinatively unsaturated metal sites for carboxylation of terminal alkynes with carbon dioxide
Wang, Wen-Jing,Sun, Zhong-Hua,Chen, Sheng-Chun,Qian, Jun-Feng,He, Ming-Yang,Chen, Qun
, (2021/05/24)
The development of efficient and stable metal–organic framework (MOF) catalysts with coordinatively unsaturated metal sites for modern organic synthesis is greatly important. Herein, a robust [Cu4(μ3-OH)2]-cluster-based MOF (Cu-MOF) with a mixed-ligand system was successfully fabricated by a microwave-assisted method under mild conditions. The as-prepared Cu-MOF catalyst possessing unsaturated Cu (II) sites exhibited excellent catalytic activity toward the direct carboxylation of 1-ethynylbenzene with CO2, and various propiolic acid derivatives were synthesized in moderate to good yields under optimized reaction conditions. Furthermore, the catalyst remained stable and could be easily recycled for five sequential runs without incredible decrease in catalytic efficiency.
Oxidant- and additive-free simple synthesis of 1,1,2-triiodostyrenes by one-pot decaroboxylative iodination of propiolic acids
Ghosh, Subhankar,Ghosh, Rajat,Chattopadhyay, Shital K.
supporting information, (2020/09/15)
A metal- and oxidant-free facile synthesis of a range of 1,1,2-triiodostryrene derivatives has been developed which utilizes a simple decarboxylative triiodination of propiolic acids using molecular iodine and sodium acetate in a one-pot manner. Electron-
Visible light induced 3-position-selective addition of arylpropiolic acids with ethersviaC(sp3)-H functionalization
Luo, Jun,Wan, Zi-Juan,Yuan, Xiao-Feng
supporting information, p. 3258 - 3262 (2020/05/14)
Although the 2-position-selective decarboxylative coupling or addition of arylpropiolic acids with cyclic ethers has been intensively investigated, selective functionalization of arylpropiolic acids at the 3-position is still a big challenge. Herein, an i
NiCl2-catalyzed radical cross decarboxylative coupling between arylpropiolic acids and cyclic ethers
Wan, Zi-juan,Wang, Jin-yuan,Luo, Jun
supporting information, p. 613 - 616 (2019/01/29)
A direct alkenylation of cyclic ethers via radical cross decarboxylative coupling process catalyzed by NiCl2 and using DTBP as radical initiator and oxidant was developed. A variety of arylpropiolic acids and cyclic ethers were transformed into the corresponding 2-arylvinyl cyclic ethers in moderate to excellent yields. Mechanistic experiments were conducted to determine the nature of the reaction intermediates, and a plausible reaction mechanism involving NiCl2-promoted radical process was proposed.
Rhodium(III)-catalysed cascade [3 + 2] annulation of: N -aryloxyacetamides with 3-(hetero)arylpropiolic acids: Synthesis of benzofuran-2(3 H)-ones
Pan, Jin-Long,Liu, Tuan-Qing,Chen, Chao,Li, Quan-Zhe,Jiang, Wei,Ding, Tong-Mei,Yan, Zhi-Qiang,Zhu, Guo-Dong
supporting information, p. 8589 - 8600 (2019/10/02)
Herein, a cascade [3 + 2] annulation of N-aryloxyacetamides with 3-(hetero)arylpropiolic acids affording benzofuran-2(3H)-ones via rhodium(iii)-catalyzed redox-neutral C-H functionalization/isomerization/lactonization using an internal oxidative directing group O-NHAc was achieved. This catalytic system provides a regio- and stereoselective approach to synthesize (Z)-3-(amino(aryl)methylene)benzofuran-2(3H)-ones with exclusive Z configuration selectivity, acceptable yields and good functional group tolerance. Preliminary investigations on ultraviolet-visible and fluorescence behaviors reveal that the annulation products may be applied as a promising fluorescent probe for sensing metal cations, especially for cerium (Ce3+).
Carboxylation of terminal alkynes promoted by silver carbamate at ambient pressure
Bresciani, Giulio,Marchetti, Fabio,Pampaloni, Guido
, p. 10821 - 10825 (2019/07/15)
Transition metal carbamates constitute a class of compounds with unique properties, however their catalytic potential has been sparingly explored so far. The easily available silver N,N-dimethylcarbamate, Ag(O2CNMe2), worked as a catalyst in the carboxylation reaction of terminal alkynes with CO2 at atmospheric pressure. Different reaction parameters (solvent, base, temperature, time and the amount of catalyst) were investigated in order to establish the optimal conditions.
Method for preparing propiolic acid and derivatives thereof under mild condition
-
Paragraph 0027; 0028; 0101; 0102, (2018/09/08)
The invention provides a novel method for preparing propiolic acid compounds through a domino reaction. The method comprises a step of subjecting terminal alkyne compounds, hydrosilane and CO2 to thedomino reaction under the catalysis action of Lewis base so as to obtain propiolic acid compounds. According to the invention, common Lewis base is used as a promoter, and corresponding propiolic acidcompounds containing different function groups can be efficiently produced through a reaction of the terminal alkyne compounds with hydrosilane and normal-pressure CO2 under a mild condition (a temperature of 40 DEG D). According to the method, CO2 is used as a raw material; the cheap Lewis base is used as the promoter; usage of precious metals is avoided; the domino reaction is employed; purification and separation of intermediates are not needed; and reaction conditions are mild. Thus, the method is an efficient cheap green synthetic method and has good industrial application value.
Sequential protocol for C(sp)–H carboxylation with CO2: KOtBu-catalyzed C(sp)–H silylation and KOtBu-mediated carboxylation
Yu, Bo,Yang, Peng,Gao, Xiang,Yang, Zhenzhen,Zhao, Yanfei,Zhang, Hongye,Liu, Zhimin
, p. 449 - 456 (2018/02/06)
CO2 incorporation into C–H bonds is an important and interesting topic. Herein a sequential protocol for C(sp)–H carboxylation by employing a metal-free C–H activation/catalytic silylation reaction in conjunction with KOtBu-mediated carboxylation with CO2 was established, in which KOtBu catalyzes silylation of terminal alkynes to form alkynylsilanes at low temperature, and simultaneously mediates carboxylation of the alkynesilanes with atmospheric CO2. Importantly, the carboxylation further promotes the silylation, which makes the whole reaction proceed very rapidly. Moreover, this methodology is simple and scalable, which is characterized by short reaction time, wide substrate scope, excellent functional-group tolerance and mild reaction conditions, affording a range of corresponding propiolic acid products in excellent yields in most cases. In addition, it also allows for a convenient 13C-labeling through the use of 13CO2.
