10271-65-5Relevant academic research and scientific papers
The first example of formation of the benzyne intermediate from the reactions of selenonium salts with phenyllithium
Kataoka, Tadashi,Watanabe, Shin-ichi,Yamamoto, Keiichirou
, p. 2153 - 2156 (1999)
The reaction of diphenyl(phenylethynyl)selenonium salt 1a with 1.0 equiv. of phenyllithium afforded 1,4-diphenylbutadiyne 5 and 1-(o- biphenylyl)-2-phenylethyne 7 in 25% and 15% yields, respectively. The latter product 7 was formed via the benzyne intermediate.
Palladium Catalysts for Cross-Coupling of Ortho-Substituted Aryl Triflates with Grignard Reagents
Kamikawa, Takashi,Hayashi, Tamio
, p. 163 - 164 (1997)
Dichloro[(2-dimethylamino)propyldiphenylphosphine]palladium (PdCl2(alaphos)) and dichloro[1,3-bis(diphenylphosphino)-propane]palladium (PdCl2(dppp)) were found to be much more effective catalysts than PdCl2(PPh3)2 and other palladium complexes for cross-coupling of sterically congested aryl triflates with aryl and alkynyl Grignard reagents.
Decarbonylative Sonogashira Cross-Coupling of Carboxylic Acids
Liu, Chengwei,Szostak, Michal
, p. 4726 - 4730 (2021)
Decarbonylative Sonogashira cross-coupling of carboxylic acids by palladium catalysis is presented. The carboxylic acid is activated in situ by the formation of a mixed anhydride and further decarbonylates using the Pd(OAc)2/Xantphos system to provide an aryl-Pd intermediate, which is intercepted by alkynes to access the traditional Pd(0)/(II) cycle using carboxylic acids as ubiquitous and orthogonal electrophilic cross-coupling partners. The methodology efficiently constructs new C(sp2)-C(sp) bonds and can be applied to the derivatization of pharmaceuticals. Mechanistic studies give support to decarbonylation preceding transmetalation in this process.
Palladium/copper-cocatalyzed decarbonylative alkynylation of acyl fluorides with alkynylsilanes: Synthesis of unsymmetrical diarylethynes
Chen, Qiang,Fu, Liyan,Nishihara, Yasushi
, p. 7977 - 7980 (2020)
Palladium/copper-cocatalyzed decarbonylative alkynylation of acyl fluorides with alkynylsilanes is described. This reaction not only effectively inhibits the formation of undesired homocoupled products by avoiding the addition of a base, but also exhibits a wide substrate scope to provide a general access to diverse unsymmetrical diarylethynes.
Cobalt(I)-catalyzed neutral Diels-Alder reactions of oxygen-functionalized acyclic 1,3-dienes with alkynes
Hilt, Gerhard,Smolko, Konstantin I.,Lotsch, Bettina V.
, p. 1081 - 1084 (2002)
The cobalt-catalyzed Diels-Alder reaction of alkoxy-substituted 1,3-butadienes with terminal and internal alkynes is described. While the reaction of 1-alkoxy derivatives gave the aromatic hydrocarbons upon elimination of alcohol from the alkoxy-substituted dihydroaromatic intermediates, the reactions with 2-alkoxy derivatives generated stable dihydroaromatic enol ethers in good to excellent chemical yields and good to high regioselectivities for unsymmetrical starting materials. The enol ethers can be easily hydrolysed to the corresponding β,γ-unsaturated ketones in a one pot reaction sequence or used in cyclopropanation or other subsequent chemical transformations.
Iodine-Catalyzed Methylthiolative Annulation of 2-Alkynyl Biaryls with DMSO: A Metal-Free Approach to 9-Sulfenylphenanthrenes
Chatterjee, Tanmay,Mukherjee, Nilanjana
, p. 7881 - 7890 (2021/06/28)
An iodine-catalyzed sustainable, cost-effective, and atom-economic synthetic methodology is developed to synthesize a wide variety of valuable sulfenylphenanthrenes and polycyclic heteroaromatics in moderate to high yield through electrophilic thiolative annulation of 2-alkynyl biaryls (6-endo-dig cyclization) using methyl sulfoxides such as dimethyl sulfoxide (DMSO) as the sulfur source under transition-metal-free conditions. The transformation requires only iodine in a catalytic amount and trifluoroacetic anhydride. Notably, DMSO played multiple roles such as methylthiolating reagent, oxidant, and solvent in this reaction.
Silicon as a powerful control element in HDDA chemistry: redirection of innate cyclization preferences, functionalizable tethers, and formal bimolecular HDDA reactions
Hoye, Thomas R.,Lynn, Mandy,Pierson Smela, Merrick
, p. 13902 - 13908 (2021/11/04)
The 1,3-diyne and diynophile in hexadehydro-Diels-Alder (HDDA) reaction substrates are typically tethered by linker units that consist of C, O, N, and/or S atoms. We describe here a new class of polyynes based on silicon-containing tethers that can be disposed of and/or functionalized subsequent to the HDDA reaction. The cyclizations are efficient, and the resulting benzoxasiloles are amenable to protodesilylation, halogenation, oxygenation, and arylation reactions. The presence of the silicon atom can also override the innate mode of cyclization in some cases, an outcome attributable to a β-silyl effect on the structure of intermediate diradicals. Overall, this strategy equates formally to an otherwise unknown, bimolecular HDDA reaction and expands the versatility of this body of aryne chemistry.
Metal-Free Synthesis of Selenodihydronaphthalenes by Selenoxide-Mediated Electrophilic Cyclization of Alkynes
An, Shaoyu,Li, Pingfan,Zhang, Zhong
, p. 3059 - 3070 (2021/07/22)
A transition-metal-free, selenium mediated electrophilic cyclization reaction was realized through a one-pot procedure between simple alkynes and triflic anhydride-activated selenoxides to give selenium containing dihydronaphthalene products. This method gave good to very high yields for all products, including selenium-substituted phenanthrene, dihydroquinoline, 2H-chromene, and coumarin, which can be further transformed to other functionalized compounds.
Palladium-catalyzed decarbonylative sonogashira coupling of terminal alkynes with carboxylic acids
Chen, Tieqiao,Huang, Tianzeng,Li, Chunya,Li, Wenhui,Li, Xinyi,Li, Zhaohui,Liu, Long,Tang, Zhi,Zhang, Tao
supporting information, p. 3304 - 3309 (2021/05/31)
A direct decarbonylative Sonogashira coupling of terminal alkynes with carboxylic acids was achieved through palladium catalysis. This reaction did not use overstoichiometric oxidants, thus overcoming the homocoupling issue of terminal alkynes. Under the reaction conditions, a wide range of carboxylic acids including those bioactive ones could couple readily with various terminal alkynes, thus providing a relative general method for preparing internal alkynes.
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.
