- Cobalt-Mediated Decarboxylative/Desilylative C?H Activation/Annulation Reaction: An Efficient Approach to Natural Alkaloids and New Structural Analogues
-
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
- Hai, Li,Lai, Ruizhi,Lv, Shan,Nie, Ruifang,Wu, Yong,Yang, Zhongzhen,chen, Kang
-
-
- Access to Triazolopiperidine Derivatives via Copper(I)-Catalyzed [3+2] Cycloaddition/Alkenyl C?N Coupling Tandem Reactions
-
A copper-catalyzed [3+2] cylcoaddition/ alkenyl C?N coupling tandem reaction was demonstrated. It provided a method for the formation of triazolopiperidine skeletons. (Figure presented.).
- Xiao, Guorong,Wu, Kaifu,Zhou, Wei,Cai, Qian
-
supporting information
p. 4988 - 4991
(2021/10/14)
-
- Oxidant- and additive-free simple synthesis of 1,1,2-triiodostyrenes by one-pot decaroboxylative iodination of propiolic acids
-
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-
- Ghosh, Subhankar,Ghosh, Rajat,Chattopadhyay, Shital K.
-
-
- Visible light induced 3-position-selective addition of arylpropiolic acids with ethersviaC(sp3)-H functionalization
-
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
- Luo, Jun,Wan, Zi-Juan,Yuan, Xiao-Feng
-
supporting information
p. 3258 - 3262
(2020/05/14)
-
- A Construction of α-Alkenyl Lactones via Reduction Radical Cascade Reaction of Allyl Alcohols and Acetylenic Acids
-
An iron-catalyzed cascade reaction of radical reduction of allyl alcohols and acetylenic acids to construct polysubstituted α-alkenyl lactones has been developed. In this paper, various allyl alcohols can form allyl ester intermediates and are further transformed into alkyl radicals, which form products through intramolecular reflex-Michael addition. In addition, this method can be used to prepare spirocycloalkenyl lactones. Interestingly, this protocol can be used to synthesize the skeleton structure of natural products. Moreover, the product can be further transformed into a β-methylene tetrahydrofuran and tetrahydrofuran diene.
- Zhang, Hua,Zhang, Guo-Min,He, Shuai,Shi, Zhi-Chuan,Zhang, Xiao-Mei,Wang, Ji-Yu
-
supporting information
p. 8337 - 8344
(2020/11/03)
-
- Visible Light-Catalyzed Decarboxylative Alkynylation of Arenediazonium Salts with Alkynyl Carboxylic Acids: Direct Access to Aryl Alkynes by Organic Photoredox Catalysis
-
A convenient method mediated by photoredox catalysis is developed for the direct construction of aryl alkynes. Readily available aromatic diazonium salts have been utilized as the aryl radical source to couple alkynyl carboxylic acids to feature the decarboxylative arylation. A wide range of substrates are amenable to this protocol with broad functional group tolerance, and diversely-functionalized aryl alkynes could be synthesized under mild, neutral and transition metal-free reaction conditions using visible light irradiation. Alongside synthetic sustainability associated with the photocatalytic and transition metal-free operation, another key point of this method is that the organic dye catalyst acts as an excited-state reductant, thus establishing the quenching cycle for radical addition and decarboxylative elimination. (Figure presented.).
- Yang, Liangfeng,Li, Haifeng,Du, Yijun,Cheng, Kai,Qi, Chenze
-
p. 5030 - 5041
(2019/11/03)
-
- NiCl2-catalyzed radical cross decarboxylative coupling between arylpropiolic acids and cyclic ethers
-
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.
- Wan, Zi-juan,Wang, Jin-yuan,Luo, Jun
-
supporting information
p. 613 - 616
(2019/01/29)
-
- Silver-catalyzed Double Decarboxylative Radical Alkynylation/Annulation of Arylpropiolic Acids with α-keto Acids: Access to Ynones and Flavones under Mild Conditions
-
Ynones are privileged building blocks in various organic syntheses of heterocyclic derivatives due to their multifunctional nature, and flavones are an important class of natural products with a wide range of biological activities. We describe the catalytic double decarboxylative alkynylation of arylpropiolic acids with α-keto acids. With Ag(I)/persulfate as the catalysis system, the valuable ynones bearing various substituents could be easily obtained. The introduction of hydroxyl substituent on ortho-site of α-keto acids make this strategy further applicable to the construction of flavone derivatives via heteroannulation in moderate to good yields with a similar silver-catalyzed system. The reactions proceed under relatively mild reaction conditions and tolerate a wide variety of functional groups. Control experiments indicated that both the reactions undergo radical processes. (Figure presented.).
- Meng, Mengting,Wang, Guofang,Yang, Liangfeng,Cheng, Kai,Qi, Chenze
-
p. 1218 - 1231
(2018/02/16)
-
- Method for synthesizing alpha-alkynyl substituted ether compounds
-
The invention discloses a method for preparing alpha-alkynyl substituted ether compounds. The method comprises the following steps: taking propiolic acid as a raw material, and synthesizing substituted phenylpropiolic acid under conditions of substituted iodobenzene, 1,8-diazabicyclo[5.4.0]undec-7-ene, (beta-4)-platinu and dimethyl sulfoxide; taking substituted phenylpropiolic acid and p-bromophenol as raw materials, and synthesizing p-bromophenyl substituted phenylpropiolic acid ester under the conditions of 4-dimethylaminopyridine and N,N'-Dicyclohexylcarbodiimide; and performing an alkynylation reaction on the p-bromophenyl substituted phenylpropiolic acid ester in participation of tert-butyl hydroperoxide, cesium carbonate and tetrahydrofuran, and finally synthesizing alpha-alkynyl substituted ether products. According to the method disclosed by the invention, simple and readily available acetylene esters serve as an alkynylation reagent, and the target products, namely alpha-alkynyl substituted ether compounds, are synthesized in a green and environmental-friendly manner under mild conditions. The compounds play an important role in construction of multiple medical intermediates and bio-active structures.
- -
-
Paragraph 0037; 0039
(2018/04/01)
-
- Copper-Catalyzed Decarboxylative/Click Cascade Reaction: Regioselective Assembly of 5-Selenotriazole Anticancer Agents
-
A simple and efficient Cu-catalyzed decarboxylative/click reaction for the preparation of 1,4-disubstituted 5-arylselanyl-1,2,3-triazoles from propiolic acids, diselenides, and azides has been developed. The mechanistic study revealed that the intermolecular AAC reaction of an alkynyl selenium intermediate occurred. The resulting multisubstituted 5-seleno-1,2,3-triazoles were tested for in vitro anticancer activity by MTT assay, and compounds 4f, 4h, and 4p showed potent cancer cell-growth inhibition activities.
- Cui, Fei-Hu,Chen, Jing,Mo, Zu-Yu,Su, Shi-Xia,Chen, Yan-Yan,Ma, Xian-Li,Tang, Hai-Tao,Wang, Heng-Shan,Pan, Ying-Ming,Xu, Yan-Li
-
supporting information
p. 925 - 929
(2018/02/22)
-
- Substrate-Assisted, Transition-Metal-Free Diboration of Alkynamides with Mixed Diboron: Regio- and Stereoselective Access to trans-1,2-Vinyldiboronates
-
A substrate-assisted diboration of alkynamides using the unsymmetrical pinacolato-1,8-diaminonaphthalenato diboron (pinBBdan) is described. The transition-metal-free reaction proceeds in a regio- and stereoselective fashion to exclusively afford trans-vinyldiboronates in good to excellent yields. Notably, Bdan and Bpin are installed on the α- and β-carbon atoms, respectively.
- Verma, Astha,Snead, Russell F.,Dai, Yumin,Slebodnick, Carla,Yang, Yinuo,Yu, Haizhu,Yao, Fu,Santos, Webster L.
-
supporting information
p. 5111 - 5115
(2017/04/24)
-
- Palladium-Catalyzed Synthesis of Conjugated Allenynes via Decarboxylative Coupling
-
A new strategy to access conjugated allenynes via a decarboxylative coupling of propargyl esters of propiolates has been developed. In this process, allenyl-palladium intermediates are coupled with acetylides that are generated in situ to form the conjuga
- Smith, Mary K.,Tunge, Jon A.
-
p. 5497 - 5500
(2017/10/25)
-
- Palladium-catalyzed oxidative aminocarbonylation by decarboxylative coupling: Synthesis of alkynyl amides
-
Alkynyl amides were synthesized from a palladium-catalyzed coupling reaction of alkynyl carboxylic acids and amines under carbon monoxide. The reaction was conducted with palladium(II) acetate (5 mol-%) and silver(I) oxide (1.0 equiv.) in acetonitrile at 80 °C for 1 h. This method provides good to moderate product yields and good functional group tolerance towards ketone, ester, and nitrile groups.
- Hwang, Jinil,Choi, Jinseop,Park, Kyungho,Kim, Wonyoung,Song, Kwang Ho,Lee, Sunwoo
-
p. 2235 - 2243
(2015/04/14)
-
- Structural design and synthesis of arylalkynyl amide-type peroxisome proliferator-activated receptor γ3 (PPAR γ3)-selective antagonists based on the helix12-folding inhibition hypothesis
-
Peroxisome proliferator-activated receptor γ3 (PPARγ3) antagonists are candidates for treatment of type 2 diabetes, obesity and osteoporosis. However, few rational design strategies are currently available. Here, we utilized the helix12 (H12)-folding inhi
- Ohashi, Masao,Gamo, Kanae,Tanaka, Yuta,Waki, Minoru,Beniyama, Yoko,Matsuno, Kenji,Wada, Jun,Tenta, Masafumi,Eguchi, Jun,Makishima, Makoto,Matsuura, Nobuyasu,Oyama, Takuji,Miyachi, Hiroyuki
-
-
- PROCESS FOR PREPARING A PROPIOLIC ACID OR A DERIVATIVE THEREOF
-
The invention relates to a process for preparing a propiolic acid or a derivative thereof by reacting a terminal alkyne with carbon dioxide, which comprises performing the reaction in the presence of a base and a copper complex, especially a copper (I) complex having at least one ligand, at least one of the ligands of the copper complex being selected from monodentate ligands which have an aminic or iminic nitrogen atom capable of coordination with copper, and polydentate ligands having at least two atoms or atom groups which are capable of simultaneous coordination with copper and are selected from nitrogen, oxygen, sulfur, phosphorus and carbene carbon.
- -
-
Paragraph 0147 - 0151; 0157
(2014/02/15)
-
- Ruthenium-catalyzed asymmetric [2 + 2] cycloadditions between chiral acyl camphorsultam-substituted alkynes and bicyclic alkenes
-
Ruthenium-catalyzed asymmetric [2 + 2] cycloadditions between chiral acyl camphorsultam-functionalized alkynes and bicyclic alkenes were examined, providing adducts with complete exo stereoselectivity in good overall yield and enantioselectivity (up to 99% and 166:1, respectively), as well as appreciable diastereoselectivity (up to 163:1). The diastereoselectivity showed dependence on the solvent and temperature, as well as on the substitution pattern of the reacting alkyne and bicyclic alkene components. In general, higher diastereoselectivities were observed for reactions conducted in ethereal solvents and at lower temperatures between N-propynoyl camphorsultams and bicyclic alkenes.
- Goodreid, Jordan,Villeneuve, Karine,Carlson, Emily,Tam, William
-
p. 10002 - 10012
(2015/02/19)
-
- Palladium-catalyzed sonogashira reaction for the synthesis of arylalkynecarboxylic acids from aryl bromides at low temperature
-
A variety of aryl bromides were coupled with propiolic acid in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and catalyst Pd(PPh 3)4 to afford the corresponding arylalkynecarboxylic acids in good yields at low temperature. This method showed good tolerance toward functional groups such as alkoxy, ketone, ester, aldehyde, cyano, nitro, and hydroxy. Under these conditions, propiolic acid showed higher reactivity than any other compound containing terminal alkyne groups. According to the mechanistic studies, the key reaction step for the high reactivity of propiolic acid might be ligand exchange between the acetylide and bromide at palladium, and/or reductive elimination, but not the oxidative addition step. A variety of aryl bromides were coupled with propiolic acid in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and catalyst Pd(PPh3) 4 to afford the corresponding arylpropiolic acids in good yields at low temperature.
- Park, Kyungho,You, Jung-Min,Jeon, Seungwon,Lee, Sunwoo
-
p. 1973 - 1978
(2013/05/09)
-
- Synthesis of aryl alkynyl carboxylic acids and aryl alkynes from propiolic acid and aryl halides by site selective coupling and decarboxylation
-
The coupling of propiolic acid with aryl iodides afforded the aryl alkynyl carboxylic acids and aryl alkynes in generally good yields. Aryl alkynyl carboxylic acids were obtained when the reaction was performed in the presence of Pd(PPh3)2Cl2 (2.5 mol %), dppb (5.0 mol %) and DBU (5 equiv) at 50°C. For the synthesis of the terminal aryl alkynes, the reaction was conducted in the presence of Pd(PPh3) 2Cl2 (2.5 mol %), dppb (5.0 mol %), DBU (5.0 equiv), and Cu(acac)2 (10 mol %) at 25°C for 5 h, and further reacted at 60°C for 6 h.
- Park, Kyungho,Palani, Thiruvengadam,Pyo, Ayoung,Lee, Sunwoo
-
experimental part
p. 733 - 737
(2012/03/08)
-
- Synthesis of propiolic acids via copper-catalyzed insertion of carbon dioxide into the C-H bond of terminal alkynes
-
A highly effective copper catalyst has been developed that promotes the insertion of carbon dioxide into the C-H bond of terminal alkynes under unprecedentedly mild conditions. For the first time, propiolic acids can thus be synthesized in excellent yields from alkynes and carbon dioxide in the presence of the mild base cesium carbonate. The catalyst, (4,7-diphenyl-1,10- phenanthroline)bis[tris(4-fluorophenyl)phosphine]copper(I) nitrate, is easy accessible and relatively stable against air and water. Copyright
- Goossen, Lukas J.,Rodriguez, Nuria,Manjolinho, Filipe,Lange, Paul P.
-
supporting information; experimental part
p. 2913 - 2917
(2011/02/22)
-
- SUBSTITUTED 1-PROPIOLYLPIPERAZINES HAVING AN AFFINITY FOR THE MGLUR5 RECEPTOR IN ORDER TO TREAT PAINFUL CONDITIONS
-
The invention relates to substituted 1-propiolylpiperazines according to formula (I), to a method for the production thereof, medicaments containing said compounds and to the use thereof in the production of medicaments. In formula (I), X represents N or C-R2 and n corresponds to a value between 0-8.
- -
-
Page/Page column 98-99
(2010/02/15)
-
- Enantioselective synthesis of axially chiral phthalides through cationic [Rh1(H8-binap)]-catalyzed cross alkyne cyclotrimerization
-
(Chemical equation presented). Easy access to axially chiral phthalides that bear one or two oxymethylene functionalities is provided by an enantioselective cross alkyne cyclotrimerization in the presence of the cationic complex [Rh1{(S)-H8-binap}]+. The axial chirality is introduced during the formation of the benzene ring with high enantioselectivity.
- Tanaka, Ken,Nishida, Goushi,Wada, Azusa,Noguchi, Keiichi
-
p. 6510 - 6512
(2007/10/03)
-
- Flash Vacuum Pyrolysis of Stabilised Phosphorous Ylides. Part 4. Stepwise Construction of Terminal 1,3-Diynes, Conjugated Diacetylenic Esters and a Triacetylenic Ester
-
Thirteen examples of stabilised alkynol ylides 6 have been prepared and are found, upon flash vacuum pyrolysis (FVP) at 500 deg C, to undergo extrusion of Ph3PO to give the diacetylenic esters 7 in moderate yield.At 750 deg C the same ylides afforded terminal 1,3-diynes 8 although often in poor yield.For R = 2-MeSC6H4 both 7 and 8 undergo secondary loss of Me* and cyclisation to give 2-alkynylbenzothiophene derivatives 9 and 10 in low yield.The first example of an alkadiynol ylide 11 has been prepared and is converted by FVP at 500 deg C into the triacetylenic ester 12.
- Aitken, R. Alan,Seth, Shirley
-
p. 2461 - 2466
(2007/10/02)
-
- The Preparation of Arylpropiolic Acids via Styrylisoxazoles
-
The vic-dibromo derivatives obtained by bromine addition to 3-methyl-4-nitro-5-styrylisoxazoles were used as starting materials for the preparation of arylpropiolic acids.
- Chimichi, S.,Sio, F. De,Donati, D.,Pepino, R.,Rabatti, L.,Sarti-Fantoni, P.
-
p. 105 - 107
(2007/10/02)
-