103-30-0Relevant articles and documents
Palladium-catalyzed cross-coupling of Cr(CO)3-complex chloroarenes with organofluorosilanes
Kang, Suk-Ku,Kim, Won-Yeob
, p. 3743 - 3749 (1998)
The palladium-catalyzed cross-coupling of (η6-chlorobenzene) tricarbonylchromium complexes with organofluorosilanes followed by decomplexation afforded aryl-, alkenyl-, and alkynyl-substituted arenes.
Tandem Hydrosilylation/o-C-H Silylation of Arylalkynes Catalyzed by Ruthenium Bis(silyl) Aminophosphine Complexes
Kitano, Takeo,Komuro, Takashi,Ono, Rikima,Tobita, Hiromi
, p. 2710 - 2713 (2017)
An unprecedented reaction via consecutive trans-selective hydrosilylation and o-C-H silylation of arylalkynes with hydrosilanes was developed by use of ruthenium complex catalysts Ru{?°3(Si,O,Si)-xantsil}(CO)(PR3) (R = NC4H8 (1-Pyrr), NC5H10 (1-Pip); xantsil = (9,9-dimethylxanthene-4,5-diyl)bis(dimethylsilyl)). This reaction proceeded with gentle heating at 40-60 °C and afforded novel 2,α-bis-silylated (Z)-stilbene or (Z)-styrene derivatives 2 together with an equimolar amount of (E)-/(Z)-arylalkenes as byproducts. The selectivity of the formation of 2 reached a maximum by employing catalyst 1-Pyrr ligated by the less bulky triaminophosphine P(NC4H8)3 and hydrosilane HSiMe(OSiMe3)2 having moderately bulky and electron withdrawing substituents.
Pascali,Umani-Ronchi
, p. 351 (1973)
Manganese chloride-catalyzed cross-coupling and carbonylative cross- coupling of organostannanes with iodonium salts
Kang, Suk-Ku,Kim, Won-Yeob,Lee, Yong-Tack,Ahn, Sung-Ki,Kim, Jin-Chul
, p. 2131 - 2132 (1998)
The MnCl2-4H2O-catalyzed cross-coupling and carbonylative cross- coupling of organostannanes with hypervalent iodonium salts afforded biaryls and biaryl ketones, respectively.
Palladium-catalyzed cross-coupling of triarylbismuth(V) derivatives with hypervalent iodonium salts
Kang,Ryu,Kim
, p. 1021 - 1026 (2001)
The palladium-catalyzed cross-coupling of hypervalent iodonium salts with organobismuth(V) derivatives was accomplished with PdCl2 (5 mol%) in CH3CN at room temperature.
Fluoride-promoted cross-coupling of chloro(mono-, di-, or triphenyl)germanes with aryl halides in "moist" toluene. Multiple transfer of the phenyl group from organogermane substrates and comparison of the coupling efficiencies of chloro(phenyl)germanes with their corresponding stannane and silane counterparts
Pitteloud, Jean-Philippe,Zhang, Zun-Ting,Liang, Yong,Cabrera, Laura,Wnuk, Stanislaw F.
, p. 8199 - 8212 (2010)
The trichlorophenyl-, dichlorodiphenyl-, and chlorotriphenylgermanes undergo Pd-catalyzed cross-couplings with aryl bromides and iodides in the presence of tetrabutylammonium fluoride in toluene with addition of the measured amount of water. One chloride ligand on the Ge center allows efficient activation by fluoride to promote transfer of one, two, or three phenyl groups from the organogermanes. The corresponding chlorophenylstannanes were found to be more reactive than chlorophenylsilanes, which in turn were more effective than chlorophenylgermanes. One chloride ligand on the Ge or Si center allows efficient activation by fluoride to promote transfer of up to three aryl groups from germane or silicon. However, no haloligand was necessary to be present on the Sn center, since tetraphenyltin efficiently transferred up to four phenyl groups during fluoride-promoted couplings with aryl halides. 19F NMR studies suggested formation of the fluorophenylgermanes and the hypervalent germanate species as possible intermediates.
CARBODETELLURATION OF ARYLTELLURIUM(IV) COMPOUNDS: OLEFIN ARYLATION AND AROMATIC COUPLING
Uemura, Sakae,Wakasugi, Mikio,Okano, Masaya
, p. 277 - 284 (1980)
Aryltellurium(IV) compounds react with olefins to give the corresponding arylated olefins in moderate to quantitative yield in the presence of a palladium(II) salt.The reaction proceeds catalytically with respect to the palladium(II) salt if a suitable oxidant, such as t-butyl hydroperoxide or copper(I) or (II) chloride, is added.In the absence of olefin the corresponding biaryls are formed in moderate yield.Transmetalation of tellurium with palladium is a key step of the reaction.
Synthesis and characterization of pyrazolyl-functionalized imidazolium-based ionic liquids and hemilabile (Carbene)palladium(II) complex catalyzed heck reaction
Wang, Ruihu,Zeng, Zhuo,Twamley, Brendan,Piekarski, Melissa M.,Shreeve, Jean'ne M.
, p. 655 - 661 (2007)
Neat reactions of 1-(pyrazolylmethyl)imidazole with an excess of alkyl or polyfluoroalkyl halides at 100°C followed by subsequent metathetical reactions with LiN(SO2CF3)2 or KPF6 at 25°C gave rise to a series of
Palladium-catalyzed cross-coupling of organoboron compounds with iodonium salts and iodanes
Kang, Suk-Ku,Lee, Hong-Woo,Jang, Su-Bum,Ho, Pil-Su
, p. 4720 - 4724 (1996)
The palladium-catalyzed cross-coupling reaction of iodinanes (iodonium salts and iodanes) with organoboron compounds to form carbon-carbon bonds was achieved at ambient temperature under aqueous conditions in the absence of base. Coupling of phenylboronic acid with diphenyliodonium tetrafluoroborate in the presence of Pd(PPh3)4 (0.2 mol %) or Pd(OAc)2 (0.2 mol %) under aqueous conditions gave biphenyl in almost quantitative yield. Under the same conditions, substituted boronic acids, boronates, and trialkylboranes were readily coupled with diaryl-, alkenyl-, and alkynyliodonium salts. Finally, the iodanes ArI(OH)OTs underwent cross-coupling with boronic acids, boronates, and trialkylboranes to afford biphenyls and aryl-substituted alkenes.
A Convenient Reagent for the Intermolecular Coupling of Aldehydes and Ketones to Form Olefins
Carroll, Anthony R.,Taylor, Walter C.
, p. 1439 - 1443 (1990)
When aldehydes or ketones are treated with titanium tetrachloride and amalgamated magnesium turnings in tetrahydrofuran at 0 deg C for 2 h and subsequently under reflux for 24 h, reductive coupling occurs to give olefin in high yield.The optimum ratio of carbonyl substrate to titanium reagent was found to be 1 : 4.Examples of symmetrical and mixed couplings are given.Intramolecular coupling was not successful.
Electron-transfer Reduction of Protons to Hydrogen mediated by a Phenyl-lithium-activated Fe4S4 Cluster
Inoue, Hiroo,Sato, Makoto
, p. 1014 - 1015 (1982)
A synthetic Fe4S4 cluster mediates the transfer of electrons from phenyl-lithium to protons from benzenethiol, in a homogeneous system, resulting in the generation of hydrogen.
Isomerization Behavior of Halostilbene Radical Cations in the Excited States. Two-Color Photochemistry of Stilbene Derivatives
Kuriyama, Yasunao,Hashimoto, Fumiko,Tsuchiya, Masahiro,Sakuragi, Hirochika,Tokumaru, Katsumi
, p. 1371 - 1374 (1994)
Two-color laser excitation of (Z)-4,4'-dichlorostilbene and (Z)-4,4'-difluorostilbene with 425- and 500-nm laser pulses in acetonitrile containing 9,10-dicyanoanthracene and biphenyl exhibited a spectral change indicating a rapid conversion of the Z-radic
A First Palladium-Catalyzed Aryldegermylation of Styryltrimethylgermanes
Ikenaga, Kazutoshi,Matsumoto, Satoshi,Kikukawa, Kiyoshi,Matsuda, Tsutomu
, p. 185 - 188 (1990)
Both β-(E)- and β-(Z)-styryltrimethylgermanes easily reacted with arenediazonium tetrafluoroborates under palladium catalysis to give aryldegermylated products, (E)-PhCH=CHAr and Ph(Ar)C=CH2.On the other hand, the aryldegermylation of α-styrylgermane gave (E)-stilbene derivates with high stereo- and regioselectivities.
Cobalt-catalyzed alkenylation of organomagnesium reagents
Cahiez, Gerard,Avedissian, Hovsep
, p. 6159 - 6162 (1998)
Alkenyl iodides, bromides and chlorides react with organomagnesium reagents in THF, in the presence of Co(acac)2 and NMP (9 to 4 equiv.), to give the cross-coupling products in good yields. The reaction is chemoselective (aryl or alkyl bromides, esters and ketones) and stereoselective (≤ 99.5%).
Akiyama et al.
, p. C7 (1977)
Mathai,Miller
, p. 3416,3417-3419 (1970)
Selective Isomerization of cis-Stilbene by Non-Resonant Two-Photon Excitation
Miyazawa, Takashi,Koshihara, Shin-ya,Segawa, Yusaburo,Kira, Mitsuo
, p. 217 - 218 (1995)
Non-Resonant two-photon excitation induced dramatical cange in the photoreaction pathways of stilbenes.Typically, irradiation of cis-stilbene with 532 nm laser pulses caused only isomerization to trans-stilbene in hexane at room temperature; the cyclization to dihydrophenanthrene was completely suppressed.
THE PALLADIUM-CATALYZED "HEAD-TO-TAIL" CROSS-COUPLING REACTION OF 1-ALKENYLBORANES WITH PHENYL OR 1-ALKENYL IODIDES. A NOVEL SYNTHESIS OF 2-PHENYL-1-ALKENES OR 2-ALKYL-1,3-ALKADIENES VIA ORGANOBORANES
Miyaura, Norio,Suzuki, Akira
, p. C53 - C56 (1981)
The reaction of phenyl or 1-alkenyl iodides with 1-alkenyl-1,3,2-benzodioxaboroles readily obtainable via the hydroboration of 1-alkynes, gives the corresponding "head-to-tail" cross-coupling products, 2-phenyl-1-alkenes or 2-alkyl-1,3-alkadienes, in good yields.The reaction is effectively catalyzed by catalytic amounts of palladium compounds in the presence of triethylamine.
Heterotriangulene as an electron-transfer mediator in reduction of vic-dibromide compounds
Inagi, Shinsuke,Kaihatsu, Noriyuki,Kuribayashi, Shunsuke,Fuchigami, Toshio
, p. 846 - 848 (2013)
A novel heterotriangulene derivative and its nonfused analogue were successfully prepared, and their electrochemical and optical properties were studied by cyclic voltammetry measurements and UVvis and photoluminescence analyses. The mediatory use of the heterotriangulene derivative for the electrocatalytic reduction of dibromo compounds was also investigated.
Synthesis of xylylene-bridged dipalladium complexes with imidazole and triazole-based di-N-heterocyclic carbene (NHC) ligands
Du, Yufeng,Tang, Huiling,Ding, Hong,Shi, Yanhui,Cao, Changsheng,Pang, Guangsheng
, p. 735 - 739 (2016)
The di-N-heterocyclic carbene (NHC) dipalladium complexes, [(PdPyBr2)2(di-NHCimi)] and [(PdPyBr2)2(di-NHCtri)], di-NHCimi and di-NHCtri represent an imidazolylidene and a triazolylidene, respectively, featuring a 1,4-xylylene spacer between the carbene units, have been prepared. The influences of the imidazolylidene and triazolidene backbone and different substituents on the catalytic activity have been investigated in the Mizoroki-Heck reaction of styrene with bromobenzene.
Palladium on calcium carbonate combined to 2-hydroxypropyl-α/β- cyclodextrins: A selective catalytic system for aqueous heck coupling and hydroarylation
Senra, Jaqueline D.,Malta, Luiz Fernando B.,Souza, Andrea Luzia F.,Aguiar, Lucia C. S.,Antunesa
, p. 2551 - 2558 (2008)
An efficient, selective and recoverable catalytic system for ligand-free aqueous Heck reactions using hydroxypropylated cyclodextrins (HPCDs) and palladium on calcium carbonate (Pd/CaCO3) is highlighted. Remarkably, stereo- and chemoselectivities could be tuned by the cavity size of cyclodextrins, exploiting the relevance of host-guest interactions. UVVis experiments have led to strong evidence concerning an interplay between Pd(II) and α-HPCD, possibly ascribed to a reduction/stabilization effect of CDs. Unexpectedly, hydroarylation was the favored pathway with acrylonitrile which provided access to 3-phenylpropionitrile derivatives without usual hydride donors. Finally, determination of soluble Pd(0/II) via AAS enabled the definition of a predominant homogeneous mechanism in which TONs over 5000 were observed.
A Novel and Efficient Route to (E)-Alk-1-enyl Boronic Acid Derivatives from (E)-1-(Trimethylsilyl)alk-1-enes and a Formal Suzuki-Miyaura Cross-coupling Reaction starting with Vinylsilanes
Farinola, Gianluca M.,Fiandanese, Vito,Mazzone, Luigia,Naso, Francesco
, p. 2523 - 2524 (1995)
A novel and highly efficient conversion of vinylsilanes into vinyl boronates is described together with their Suzuki-Miyaura cross-coupling reaction, performed without isolating the intermediate resulting from borodesilylation.
Efficient PEPPSI-themed palladium N-heterocyclic carbene precatalysts for the mizoroki-heck reaction
Lin, Yong-Chieh,Hsueh, Hsin-Hsueh,Kanne, Shanker,Chang, Li-Kuang,Liu, Fu-Chen,Lin, Ivan J. B.,Lee, Gene-Hsiang,Peng, Shie-Ming
, p. 3859 - 3869 (2013)
Two sets of six PEPPSI (pyridine enhanced precatalyst preparation, stabilization, and initiation) themed palladium complexes of amide-functionalized N-heterocyclic carbenes [PdBr2(NHC)(Py)], where NHC = 1-acetamido-3-R-imidazolin-2-ylidene, 1-acetamido-3-R-benzimidazolin-2- ylidene and Py = pyridine, were prepared. Solid-state structures of all these complexes were determined by single-crystal X-ray diffraction methods. All complexes under scrutiny were found to adopt a trans arrangement with square-planar geometry. These complexes showed excellent catalytic activity toward the Mizoroki-Heck cross-coupling reaction of aryl chlorides and styrene. Benzimidazole-derived complexes exhibited better catalytic activity than imidazole-based complexes. Formation of palladium nanoparticles in the reaction mixture was evidenced by dynamic light scattering and transmission electron microscopy studies and a mercury poisoning experiment, suggesting the possible involvement of palladium nanoparticles in the catalytic reactions.
Reactions of polyfluorinated cyclohexadienones with diazoalkanes. Part 1. Formation of cyclopropanes from polyfluorinated cyclohexa-2,4-dienones with diazomethane and phenyldiazomethane
Kovtonyuk, Vladimir N.,Kobrina, Ljubov S.,Gatilov, Yurij V.,Bagryanskaya, Irina Yu.,Froehlich, Roland,Haufe, Guenter
, p. 1929 - 1933 (2000)
The reaction of 6-chloro-2,3,4,5,6-pentafluorocyclohexa-2,4-dienone (1) with diazomethane gives a mixture of two diastereoisomers of 6-chloro-3a,4,5,6,7a-pentafluoro-3,3a,6,7a-tetrahydrospiro[indazole-7,2′-o xirane] 2a and 2b. In contrast phenyldiazomethane reacts with polyfluorinated cyclohexa-2,4-dienones 1, 9, and 10 in acetonitrile to form the fluorinated 7-phenylbicyclo[4.1.0]hept-4-en-2-ones 4a,b, 11a,b, and 12a,b as the main products. This reaction shows a remarkable dependence on the polarity of the solvent. While a complex mixture of products was formed in pentane, the reaction in acetonitrile proceeds with high stereoselectivity giving only the two endo-isomers.
Utilization of microwave heating in the McMurry reaction for facile coupling of aldehydes and ketones to give alkenes
Stuhr-Hansen, Nicolai
, p. 5491 - 5494 (2005)
Microwave heating was applied in high-yield syntheses of alkenes by McMurry coupling of aldehydes and ketones with low-valent titanium. All aldehydes and ketones including sulfur end-capped analogues gave alkenes in isolated yields above 80% without detectable amounts of pinacols.
Heterobimetallic Pd/Mn and Pd/Co complexes as efficient and stereoselective catalysts for sequential Cu-free Sonogashira coupling–alkyne semi-hydrogenation reactions
Baweja, Saral,Clauss, Reike,Gelman, Dmitri,Hey-Hawkins, Evamarie
, p. 1344 - 1356 (2022/02/03)
A series of heterobimetallic PdII/MII complexes (MII = Mn, Co) were synthesised and tested as precatalysts for sequential Sonogashira coupling–alkyne semi-hydrogenation reactions to form Z-aryl alkenes. The carbometalated heterobimetallic PdII/CoII complex CoPdL3′ demonstrated an apparent cooperative effect compared to the corresponding monometallic counterparts. This compound was identified as a potent single-molecule catalyst for the one-pot Cu-free Sonogashira coupling of aryl bromides with terminal alkynes followed by chemo- and stereoselective semi-hydrogenation of the alkyne intermediate using NH3·BH3 as a hydrogen source. Furthermore, different aromatic substrates have been tested to show the generality of the reaction for the synthesis of Z-alkenes, including biologically active combretastatin A-4. In addition, the homogeneous nature of the catalytically active species was demonstrated.
Catalytic Hydrogenation of Alkenes and Alkynes by a Cobalt Pincer Complex: Evidence of Roles for Both Co(I) and Co(II)
Alawisi, Hussah,Arman, Hadi D.,Tonzetich, Zachary J.
, p. 1062 - 1070 (2021/04/09)
The Co(I) complex, [Co(N2)(CyPNP)] (CyPNP = anion of 2,5-bis-(dicyclohexylphosphinomethyl)pyrrole), is active toward the catalytic hydrogenation of terminal alkenes and the semi-hydrogenation of internal alkynes under 2 bar of H2 (g) at room temperature. The products of alkyne semi-hydrogenation are a mixture of E- and Z-alkenes. By contrast, use of the related cobalt(I) precatalyst, [Co(PMe3)(CyPNP)], results in formation of exclusively Z-alkenes. A semi-stable Co(II) species, [CoH(CyPNP)], can also be generated by treatment of degassed solutions of [Co(N2)(CyPNP)] with H2. The CoII-hydride displays activity toward both alkene hydrogenation and isomerization, but its instability hampers implementation as a catalyst. Several species relevant to potential catalytic intermediates have been isolated and detected in solution. These compounds include alkene and alkyne adducts of Co(I) as well as a Co(III) dihydride species. Catalytic results with the compounds examined are most consistent with a process involving shuttling between Co(I) and Co(III) states. However, generation of small quantities of Co(II) during catalytic turnover appears to be responsible for the isomerization observed for alkyne semi-hydrogenation. The interplay of cobalt oxidation states within the same catalyst system is discussed in the context of mechanistic scenarios for catalytic hydrogenation.
Immobilized Pd on a NHC-functionalized metal-organic FrameworkMIL-101(Cr): An efficient heterogeneous catalyst in the heck and copper-free Sonogashira coupling reactions
Niknam, Esmaeil,Panahi, Farhad,Khalafi-Nezhad, Ali
supporting information, (2021/01/12)
A heterogeneous palladium catalyst system based on immobilization of palladium moieties on a N-heterocyclic carbene (NHC) modified metal organic framework (MOF) was developed for the Heck and copper-free Sonogashira coupling reactions. In order to prepare this catalyst system, first, MIL-101(Cr) was functionalized with NHC moieties through a post synthetic modification (PSM) approach, and then Pd metal was stabilized on the prepered MIL-101(Cr)-NHC substrate. This material was characterized using various microscopic and spectroscopic techniques and then was used as an efficient heterogeneous Pd catalyst system in the Heck and copper-free Sonogashira reactions. Results of the heterogeneity tests showed that the Pd-NHC-MIL-101(Cr) catalyst can efficiently catalyzed these coupling reactions heterogeneously and no remarkable changes observed in the morphology and structure of MIL-101(Cr) template during the reaction progress. Also, existence of palladium nanoparticles immobilized on the MOF structure affirmed by the TEM and XPS analysis confirmed the oxidation state of Pd. A variety of alkene and alkyne derivatives were synthesized in good to excellent yields using this heterogeneous Pd catalyst system under normal conditions. More importantly Pd-NHC-MIL-101(Cr) catalyst was simply recovered from the reaction medium without remarkable decreasing in its catalytic activities after five times of reusability. The ICP analysis showed the very low Pd and Cr metals leaching, representing high stability and applicability of this catalyst in Pd coupling reactions.
