54655-08-2Relevant articles and documents
Au-promoted Pd-catalyzed arylative cyclization of N,N-dimethyl-o-alkynylaniline with aryl iodides: Access to 2,3-diaryl indoles and mechanistic insight
Yuan, Kemeng,Wang, Jiwei,Wang, Feijun,Zhang, Jun
supporting information, (2021/02/01)
We have developed a Au-promoted Pd-catalyzed cyclization/cross-coupling of N,N-dimethyl-o-alkynylaniline with aryl iododes to synthesize 2,3-diarylindoles under mild and base-free conditions. A related vinyl-Au species has been isolated through Au-promoted cyclization of N,N-dimethyl-o-alkynylaniline and structurally characterized. Further study on its reactivity suggests the vinyl-Au species might be out of catalytic cycle, and PhPd(OTf)(PPh3)2 is probably the reaction intermediate.
Intramolecular Addition of a Dimethylamino C(sp 3)-H Bond across C-C Triple Bonds Using IrCl(DTBM-SEGPHOS)(ethylene) Catalyst: Synthesis of Indoles from 2-Alkynyl- N -methylanilines
Ohmura, Toshimichi,Yagi, Kaito,Torigoe, Takeru,Suginome, Michinori
supporting information, p. 3057 - 3064 (2021/06/28)
Intramolecular addition of a C(sp 3)-H bond of the dimethylamino group across the C-C triple bond in 2-alkynyl- N, N -dimethylanilines is effectively catalyzed by a new iridium complex, IrCl(DTBM-SEGPHOS)(C 2H 4), in mesitylene at 150 °C. The intramolecular C(sp 3)-H addition is followed by double-bond isomerization to afford 3-substituted indoles in good to high yields.
Metal-Free and syn-Selective Hydrohalogenation of Alkynes through a Pseudo-Intramolecular Process
Asahara, Haruyasu,Mukaijo, Yusuke,Muragishi, Kengo,Iwai, Kento,Ito, Akitaka,Nishiwaki, Nagatoshi
, p. 5747 - 5755 (2021/10/20)
A new metal-free hydrohalogenation method for alkynes has been developed, which proceeds through a pseudo-intramolecular process. In this reaction, ethynylaniline serves as a substrate to quantitatively form an anilinium salt upon treatment with hydrochloric acid. The spatial proximity facilitates the efficient electrophilic addition of HCl to the ethynyl group in syn-mode, affording the corresponding chloroalkene without overaddition. This protocol was applied to HBr and HI, and the corresponding bromo- and iodoalkenes were obtained, respectively. The obtained chloroalkene was converted to tri-substituted alkenes possessing different aryl/alkynyl groups through Pd-catalyzed cross-coupling reactions.
Copper-Catalyzed Three-Component Carboamination of Arynes: Expeditious Synthesis of o-Alkynyl Anilines and o-Benzoxazolyl Anilines
Niu, Sheng-Li,Hu, Jiangtao,He, Kuicheng,Chen, Ying-Chun,Xiao, Qing
supporting information, p. 4250 - 4254 (2019/06/07)
A copper-catalyzed three-component reaction of in situ formed arynes, terminal alkynes, and O-benzoylhydroxylamines has been developed. By adjusting reaction conditions, the nucleophiles in this transformation can be extended from terminal alkynes to benzoxazoles. These procedures provide a modular and facile approach to o-alkynyl anilines and o-benzoxazolyl anilines from easily available substrates in only one step.
Palladium-Catalyzed Synthesis of 2,3-Diaryl- N-methylindoles from ortho-Alkynylanilines and Aryl Pinacol Boronic Esters
Luo, Yue-Gui,Basha, R. Sidick,Reddy, Daggula Mallikarjuna,Xue, Yong-Jing,Chen, Te-Hsuan,Lee, Chin-Fa
supporting information, p. 6872 - 6876 (2018/11/21)
A palladium-catalyzed synthesis of 2,3-diaryl-N-methylindoles from o-alkynylanilines and aryl pinacol boronic esters was developed. The system possesses high functional group tolerance and a broad substrate scope with a variety of aryl pinacol boronic est
BCl3-Induced Annulative Oxo- and Thioboration for the Formation of C3-Borylated Benzofurans and Benzothiophenes
Warner, Andrew J.,Churn, Anna,McGough, John S.,Ingleson, Michael J.
supporting information, p. 354 - 358 (2016/12/30)
BCl3-induced borylative cyclization of aryl-alkynes possessing ortho-EMe (E=S, O) groups represents a simple, metal-free method for the formation of C3-borylated benzothiophenes and benzofurans. The dichloro(heteroaryl)borane primary products can be protected to form synthetically ubiquitous pinacol boronate esters or used in situ in Suzuki–Miyaura cross couplings to generate 2,3-disubstituted heteroarenes from simple alkyne precursors in one pot. In a number of cases alkyne trans-haloboration occurs alongside, or instead of, borylative cyclization and the factors controlling the reaction outcome are determined.
Synthesis of: N -alkyl-3-sulfonylindoles and N -alkyl-3-sulfanylindoles by cascade annulation of 2-alkynyl- N, N -dialkylanilines
Meesin, Jatuporn,Pohmakotr, Manat,Reutrakul, Vichai,Soorukram, Darunee,Leowanawat, Pawaret,Kuhakarn, Chutima
supporting information, p. 3662 - 3669 (2017/07/07)
An efficient and metal-free approach to N-alkyl-3-sulfonylindoles and N-alkyl-3-sulfanylindoles from 2-alkynyl-N,N-dialkylanilines has been developed. In the presence of iodine and tert-butylhydroperoxide (TBHP), a variety of 2-alkynyl-N,N-dialkylanilines underwent a cascade radical annulation to yield 3-arylsulfonylindoles. In contrast, 3-arylsulfanylindoles were conveniently prepared by iodine mediated electrophilic annulation reactions. The present protocol uses the economical and environmentally friendly I2-TBHP or I2 system, and potentially bioactive N-alkyl-3-sulfonylindoles and N-alkyl-3-sulfanylindoles with various functional groups were successfully synthesized in moderate to good yields.
Pd/phenanthroline-catalyzed arylative cyclization of o-(1-alkynyl)thioanisoles: Synthesis of 3-arylated benzo[b]thiophenes
Yamauchi, Takayuki,Shibahara, Fumitoshi,Murai, Toshiaki
supporting information, p. 2945 - 2948 (2016/07/06)
The arylative cyclization of o-(1-alkynyl)thioanisoles with aryl iodides in the presence of catalytic amounts of [Pd(phen)2][PF6]2resulted in the efficient formation of 3-arylated benzo[b]thiophenes, and a range of aryl iodides with electron-donating or -withdrawing groups could be used. While this reaction proceeded in the presence of aromatic and aliphatic groups on the terminal alkynyl carbon atom, silyl and alkoxycarbonyl groups hampered the reaction. Furthermore, this method could be extended to the synthesis of 3-arylated indoles from N,N-dimethyl-o-(1-alkynyl)aniline. All these reactions proceeded smoothly via cleavage of the carbon-heteroatom bond. In addition to the desired cyclization products, the use of a o-(hydroxypropyl)phenylmethyl substituent on the sulfur atom afforded isochroman, which should be formed by the intramolecular attack of a hydroxy group onto the benzylic carbon atom.
Position of substitution: A facile way to tune the spectroscopic properties of dimethylamino-substituted arylene-ethynylenes
Fang, Jing-Kun,Sun, Tengxiao,Fang, Yu,Xu, Zhimin,Zou, Hui,Liu, Yuan,Ge, Fangting
, p. 487 - 491 (2015/11/03)
A series of dimethylamino-substituted arylene-ethynylenes were synthesised by Sonogashira coupling reactions and characterised by the methods of 1H, 13C NMR, UV-Vis, fluorescence, HRMS and theoretical calculations. Effects on spectroscopic properties caus
Pd/C-catalyzed cyclizative cross-coupling of two ortho-alkynylanilines under aerobic conditions: Synthesis of 2,3′-bisindoles
Yao, Bo,Wang, Qian,Zhu, Jieping
supporting information, p. 7413 - 7416 (2015/05/13)
Abstract A palladium-catalyzed cyclizative cross-coupling of two o-alkynylanilines to 2,3′-bisindoles under aerobic oxidative conditions was developed. Mechanistic studies suggested that the two catalytic cycles, namely the formation of 3-alkynylindoles 8
