144479-03-8Relevant articles and documents
Graphitic Carbon Nitride Polymer as a Recyclable Photoredox Catalyst for Decarboxylative Alkynylation of Carboxylic Acids
Guo, Jiaqi,Wang, Yating,Li, Yuhang,Lu, Kailin,Liu, Shihui,Wang, Wei,Zhang, Yongqiang
supporting information, p. 3898 - 3904 (2020/08/07)
Visible-light-induced heterogeneous photocatalysis for decarboxylative alkynylation has been performed. The using of cheap, metal-free and recyclable graphitic carbon nitride (g-C3N4) as the photoredox catalyst in the process enables
Exploring bis(cyclometalated) ruthenium(II) complexes as active catalyst precursors: Room-temperature alkene-alkyne coupling for 1,3-diene synthesis
Zhang, Jing,Ugrinov, Angel,Zhang, Yong,Zhao, Pinjing
supporting information, p. 8437 - 8440 (2014/08/18)
Described is the development of a new class of bis(cyclometalated) ruthenium(II) catalyst precursors for C-C coupling reactions between alkene and alkyne substrates. The complex [(cod)Ru(3-methallyl)2] reacts with benzophenone imine or benzophe
Iron(II) chloride catalyzed alkylation of propargyl ethers: Direct functionalization of an sp3 C-H bond adjacent to oxygen
Xie, Yongju,Yu, Ming,Zhang, Yuhong
supporting information; experimental part, p. 2803 - 2809 (2011/10/09)
Iron(II) chloride catalyzed direct alkylation of sp3 C-H bond adjacent to oxygen in propargyl ethers has been accomplished by the use of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as oxidant under mild reaction conditions. The reaction proceeded smoothly with a variety of 1,3-diketones leading to -dicarbonyl ether in moderate yields. In the absence of 1,3-diketones, ynenones were produced by the use of iron(III) chloride and DDQ. Georg Thieme Verlag Stuttgart - New York.
Electrophilic chemistry of propargylic alcohols in imidazolium ionic liquids: Propargylation of arenes and synthesis of propargylic ethers catalyzed by metallic triflates [Bi(OTf)3, Sc(OTf)3, Yb(OTf) 3], TfOH, or B(C6F5)3
Aridoss, Gopalakrishnan,Sarca, Viorel D.,Ponder Jr, James F.,Crowe, Jessica,Laali, Kenneth K.
experimental part, p. 2518 - 2529 (2011/05/13)
Metallic triflates M(OTf)3 (M = Bi, Sc, Yb), immobilized in imidazolium ionic liquids [BMIM][BF4], [BMIM][PF6] and [BMIM][OTf] are efficient systems for one-pot reactions of propargylic alcohols 1,3-diphenyl-2-propyn-1-ol Ia, 1-methyl-3-phenyl-2-propyn-1-ol Ib, and 2-pentyn-1-ol Ic, with a wide range of arenes bearing activating substituents, under mild conditions. The [BMIM][PF6]/B(C6F 5)3 and [BMIM][PF6]/TfOH systems were superior in propargylation with Ib and Ic, while reaction of 3-phenyl-2-propyn-1-ol Id with activated aromatics resulted in the formation of diaryl-propanones instead. Propargylation of anisole with Ib under M(OTf)3 catalysis is highly para selective, but with TfOH or B(C6F5)3 as catalyst the ortho isomer was also formed. Steric influence of the propargylic moiety on substrate selectivity is reflected in the lack of ortho propargylation for phenol and ethylbenzene by using propargylic alcohol Ia, and notable formation of the ortho isomer employing alcohol Ib. In the later case para selectivity could be increased by running the reaction at r. t. for 10 h. The Bi(OTf)3-catalyzed reaction of 1,3-dimethoxybenzene with Ia led to minor formation of dipropargylated derivative, along with the monopropargyl product. Propargylation of the less reactive arenes (mesitylene, ethylbenzene, toluene), using Sc(OTf)3 as catalyst, led increasingly to the formation of dipropargylic ethers and propargyl ketones, with no ring propargylation product with toluene. Concomitant formation of dipropargylic ether was also observed in Yb(OTf)3-catalyzed propargylation of β-naphthol, whereas propargylation of 2-nitro and 4-nitro-aniline led to N-propargylation. The recycling/reuse of the IL was demonstrated in representative cases with no appreciable decrease in the conversions over 3 cycles. It was also shown that recycled IL could be used to propargylate a different aromatic compound. The efficacy of IL/M(OTf)3 and IL/TfOH systems for cross-breeding two propargylic alcohols or a propargylic alcohol with a non-propargylic alcohol and/or self-coupling, to form a wide variety of functionalized ethers is also demonstrated.
Gold(I)-catalyzed rearrangement of propargyl benzyl ethers: A practical method for the generation and in situ transformation of substituted allenes
Bolte, Benoit,Odabachian, Yann,Gagosz, Fabien
supporting information; experimental part, p. 7294 - 7296 (2010/08/05)
A series of benzyl propargyl ethers react with a gold(I) catalyst to furnish variously substituted allenes via a 1,5-hydride shift/fragmentation sequence. This transformation is rapid and practical. It can be performed under very mild conditions (room temperature or 60 °C) using terminal as well as substituted alkyne substrates bearing a primary, secondary, or tertiary benzyl ether group. The allenes thus formed can be reacted in situ with an internal or external nucleophile, corresponding to an overall reductive substitution process, to produce more functionalized compounds.
A copper- and amine-free Sonogashira reaction employing aminophosphines as ligands
Cheng, Jiang,Sun, Yanhui,Wang, Feng,Guo, Minjie,Xu, Jian-Hua,Pan, Yi,Zhang, Zhaoguo
, p. 5428 - 5432 (2007/10/03)
An efficient Pd-catalyzed Sonogashira coupling reaction was achieved in the absence of a copper salt or amine with an inorganic base and easily prepared, air-stable aminophosphine ligands in commonly used organic solvents; good to excellent yields were ob
Palladium-Catalyzed Carbonylative Annulation of Internal Alkynes: Synthesis of 3,4-Disubstituted Coumarins
Kadnikov, Dmitry V.,Larock, Richard C.
, p. 9423 - 9432 (2007/10/03)
The palladium-catalyzed annulation of internal alkynes by o-iodophenols in the presence of CO results in exclusive formation of coumarins. No isomeric chromones have been observed. The best reaction conditions utilize the 2-iodophenol, 5 equiv of alkyne, 1 atm of CO, 5 mol% Pd(OAc)2, 2 equiv of pyridine, and 1 equiv of n-Bu4NCl in DMF at 120°C. The use of a sterically unhindered pyridine base is essential to achieve high yields. A wide variety of 3,4-disubstituted coumarins containing alkyl, aryl, silyl, alkoxy, acyl, and ester groups have been prepared in moderate to good yields. Mixtures of regioisomers have been obtained when unsymmetrical alkynes are employed. 2-Iodophenols with electron-withdrawing and electron-donating substituents and 3-iodo-2-pyridone are effective in this annulation process. The reaction is believed to proceed via (1) oxidative addition of the 2-iodophenol to Pd(0), (2) insertion of the alkyne triple bond into the aryl-palladium bond, (3) CO insertion into the resulting vinylic carbon-palladium bond, and (4) nucleophilic attack of the phenolic oxygen on the carbonyl carbon of the acylpalladium complex with simultaneous regeneration of the Pd(0) catalyst. This annulation process is the first example of intermolecular insertion of an alkyne occurring in preference to CO insertion.
Novel decomplexation method for alkyne-Co2(CO)6 complexes
Sugihara, Takumichi,Ban, Hitoshi,Yamaguchi, Masahiko
, p. 163 - 166 (2007/10/03)
A novel and general decomplexation method for alkyne-Co2(CO)6 complexes has been established, which treats the complexes with ethylenediamine in THF.
A Nickel-catalyzed carbozincation of aryl-substituted alkynes
Stuedemann, Thomas,Ibrahim-Ouali, Malika,Knochel, Paul
, p. 1299 - 1316 (2007/10/03)
The addition of dialkylzincs or diphenylzinc to substituted phenylacetylenes in the presence of catalytic amounts of Ni(acac)2 in THF:NMP mixtures produces syn-carbozincation products with good to excellent regio- and stereoselectivity. After quenching with an electrophile (iodine, acyl chloride, allyl bromide) tetrasubstituted olefines are obtained in good to satisfactory yields. An intramolecular version of the reaction is possible using a terminal triple bond bearing an iodine at a remote position. More substituted iodo-alkynes furnish only reductive elimination products. An application to a stereoselective synthesis of (Z)-tamoxifen (Z:E > 99:1) has been developed.
A novel method of C-C bond formation via phenylation of terminal acetylenes by triphenylbismuth difluoride
Lermontov, Sergei A.,Rakov, Igor M.,Zefirov, Nikolai S.,Stang, Peter J.
, p. 4051 - 4054 (2007/10/03)
Terminal acetylenes readily undergo phenylation by Ph3BiF2 in the presence of catalytic amounts of CuCl affording phenyl substituted acetylenes.
