197250-99-0Relevant articles and documents
An Enzymatic Platform for Primary Amination of 1-Aryl-2-alkyl Alkynes
Liu, Zhen,Qin, Zi-Yang,Zhu, Ledong,Athavale, Soumitra V.,Sengupta, Arkajyoti,Jia, Zhi-Jun,Garcia-Borràs, Marc,Houk,Arnold, Frances H.
supporting information, p. 80 - 85 (2022/01/08)
Propargyl amines are versatile synthetic intermediates with numerous applications in the pharmaceutical industry. An attractive strategy for efficient preparation of these compounds is nitrene propargylic C(sp3)-H insertion. However, achieving this reacti
Z-Selective Synthesis of α-Sulfanyl Carbonyl Compounds from Internal Alkynes and Thiols via Photoredox Catalysis
Luridiana, Alberto,Frongia, Angelo,Scorciapino, Mariano Andrea,Malloci, Giuliano,Manconi, Barbara,Serrao, Simone,Ricci, Pier Carlo,Secci, Francesco
supporting information, p. 124 - 131 (2021/10/12)
A synthetically useful Z-selective cascade formal thiyl radical addition, 1,3-double bond isomerization, oxygen trapping reaction, can be promoted by Eosin B under visible light, leading to the construction of 2-aryl- and alkylthio enone derivatives in good yields. An accurate study on the reactivity of different thiols and the screening of the reaction conditions, allowed us to extend this reaction to a large number of substrates, showing a good functional groups tolerance while highlighting the limitations of this procedure. Background experiments and mechanistic studies were also. performed to rationalize this cascade process. The usefulness of this methodology was finally demonstrated via the transformation of a series of α-sulfanyl-enone adducts through selected oxidation reactions, stereoselective synthesis of cyclopropyl ketones, indanones, and pyrazole compounds. (Figure presented.).
Hydromagnesiation of 1,3-Enynes by Magnesium Hydride for Synthesis of Tri- and Tetra-substituted Allenes
Chiba, Shunsuke,Li, Yihang,Pang, Jia Hao,Takita, Ryo,Wang, Bin,Watanabe, Kohei
, p. 217 - 221 (2020/11/30)
A protocol for regio-controlled hydromagnesiation of 1,3-enynes was developed using magnesium hydride that is generated in situ by solvothermal treatment of sodium hydride (NaH) and magnesium iodide (MgI2) in THF. The resulting allenylmagnesium species could be converted into tri- and tetra-substituted allenes by subsequent treatment with various carbon- and silicon-based electrophiles with the aid of CuCN as a catalyst.
Engineering Cytochrome P450s for Enantioselective Cyclopropenation of Internal Alkynes
Chen, Kai,Arnold, Frances H.
supporting information, p. 6891 - 6895 (2020/05/14)
We report a biocatalytic platform of engineered cytochrome P450 enzymes to carry out efficient cyclopropene synthesis via carbene transfer to internal alkynes. Directed evolution of a serine-ligated P450 variant, P411-C10, yielded a lineage of engineered
Facile Access to Diverse Libraries of Internal Alkynes via Sequential Iododediazoniation/Decarboxylative Sonogashira Reaction in Imidazolium ILs without Ligand or Additive
Prabhala, Pavankumar,Savanur, Hemantkumar M.,Kalkhambkar, Rajesh G.,Laali, Kenneth K.
supporting information, p. 2061 - 2064 (2019/03/07)
Convenient access to diverse libraries of internal alkynes via decarboxylative Sonogashira reaction of alkynyl-carboxylic acids with iodoarenes, employing imidazolium-ILs as solvent, along with piperidine-appended imidazolium [PAIM][NTf2] as task-specific basic IL is demonstrated, without the need for any ligand or additive. The feasibility to perform these reactions by sequential one-pot iododediazoniation/decarboxylative Sonogashira reaction is also shown, and the scope of the methods is underscored by providing 29 examples. The potential for recycling and reuse of the IL solvent is also examined.
CsF-Mediated in Situ Desilylation of TMS-Alkynes for Sonogashira Reaction
Capani, Joseph S.,Cochran, John E.,Liang, Jianglin
, p. 9378 - 9384 (2019/07/08)
A practical and mild set of conditions for the Sonogashira reaction utilizing CsF-mediated in situ TMS-alkyne desilylation followed by Sonogashira coupling has been developed for the synthesis of a variety of alkynyl benzenes and heteroarenes in good to excellent yields. This methodology demonstrates excellent functional group tolerance and simple purification, which allows large-scale industrial applications. This one-pot protocol enables a high-yielding Sonogashira coupling with volatile alkynes by avoiding challenging isolation of free alkynes.
Multi-Metal-Catalyzed Oxidative Radical Alkynylation with Terminal Alkynes: A New Strategy for C(sp3)-C(sp) Bond Formation
Tang, Shan,Liu, Yichang,Gao, Xinlong,Wang, Pan,Huang, Pengfei,Lei, Aiwen
supporting information, p. 6006 - 6013 (2018/05/14)
A new way for C(sp3)-C(sp) cross-coupling with terminal alkynes has been developed by using a multi-metal-catalyzed reaction strategy. Alkyl radicals generated from different approaches are able to couple with terminal alkynes by judicious selection of the catalyst combination. This reaction protocol offers an efficient alternative approach for the synthesis of substituted alkynes from terminal alkynes besides traditional Sonogashira coupling. Mechanistic studies have also been carried out to clarify the role of each metal catalyst in the radical alkynylation processes. The reactions were found to go through radical reaction pathways. Synergistic cooperation of the metal catalysts is the key for controlling the reaction selectivity of alkyl radicals toward C(sp3)-C(sp) bond formation.
Palladium and copper catalyzed Sonogashira decarboxylative coupling of aryl iodides and alkynyl carboxylic acids
Maaliki, Carine,Chevalier, Yoan,Thiery, Emilie,Thibonnet, Jér?me
supporting information, p. 3358 - 3362 (2016/07/11)
A mild procedure of palladium and copper catalyzed decarboxylative cross-coupling reaction of aryl halides and alkynyl carboxylic acids has been developed. Low molecular weight acids, to introduce small building blocks, were specifically used. This method
Decarboxylative/Sonogashira-type cross-coupling using PdCl2(Cy?Phine)2
Yang, Yong,Lim, Yee Hwee,Robins, Edward G.,Johannes, Charles W.
, p. 72810 - 72814 (2016/08/09)
The PdCl2(Cy?Phine)2 precatalyst containing the meta-terarylphosphine ligand, Cy?Phine, can effectively mediate decarboxylative cross-coupling with a diverse range of (hetero-)aryl, aryl and alkyl chlorides including those with unprotected functionality. Using a facile and robust protocol, this process was extended to the first synthesis of symmetrical di(heteroaryl)alkynes via tandem Sonogashira/decarboxylative cross-coupling of heteroaryl chlorides and propiolic acid.
Copper-catalyzed C(sp2)-C(sp) Sonogashira-type cross-coupling reactions accelerated by polycyclic aromatic hydrocarbons
Xu, Wei,Yu, Bo,Sun, Huaming,Zhang, Guofang,Zhang, Weiqiang,Gao, Ziwei
, p. 353 - 356 (2015/06/02)
Copper-catalyzed Sonogashira-type reactions were dramatically accelerated by introducing a catalytic amount of polycyclic aromatic hydrocarbon additive. This novel catalytic system features low copper loading (0.5mol% Cu 5mol%), broad reaction scope a
