- METHOD FOR PRODUCING HETEROLE MULTIMER
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PROBLEM TO BE SOLVED: To provide a method for producing a heterole multimer at low cost and in high yields. SOLUTION: A method for producing a heterole multimer has a deprotonation step in which, in the presence of a deprotonation agent and a deprotonation promoter for heteroles, heteroles are deportonated, and a coupling step in which the deprotonated heteroles form a carbon-carbon bond. SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
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Paragraph 0033
(2020/03/03)
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- Palladium-catalyzed homo-coupling of heteroarylsulfoniums via borylation/Suzuki-Miyaura coupling sequence
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Palladium-catalyzed homo-coupling of heteroaryldimethylsulfoniums proceeds in the presence of bis(pinacolato)diboron and a base to yield biheteroaryls. The homo-coupling involves palladium-catalyzed borylation and the subsequent Suzuki-Miyaura coupling. As the sulfoniums were able to be prepared in situ from the corresponding heteroaryl sulfides and methyl triflate, one-pot transformations of heteroaryl sulfides into the homo-coupling products were executed. Furthermore, a facile synthesis of a highly substituted 2,2'-bibenzofuran was accomplished with a combination of Pummerer-type synthesis of 2-benzofuryl sulfide and the present homo-coupling.
- Minami, Hiroko,Nogi, Keisuke,Yorimitsu, Hideki
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p. 998 - 1007
(2019/04/26)
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- Palladium-catalyzed reductive homocoupling of aryl sulfonates via cleavage of C─O bond at room temperature
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Palladium-catalyzed reductive homocoupling of aryl sulfonates has been successfully achieved under mild conditions. This transformation is a new method for the homocoupling reaction of aryl sulfonates at room temperature via the cleavage of C─O bonds, thus providing an alternative synthesis of symmetric biaryls. The reported reductive homocoupling reaction is tolerant of many common functional groups regardless of electron-donating or electron-withdrawing nature, making this newly developed transformation important for complementing Ullmann coupling. Experimental Section. Typical procedure for the products.
- Zhong, Shuangling,Chen, Mengxin,Liu, Ge,Sun, Chenggang,Liu, Wencong
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- Synthesis of 2,5-Disubstituted Furans from Sc(OTf)3 Catalyzed Reaction of Aryl Oxiranediesters with γ-Hydroxyenones
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A convenient synthesis of 2,5-disubstituted furan was developed by employing donor-acceptor oxiranes in a new reaction with γ-hydroxyenones. Sc(OTf)3 was found to be the best catalyst, and 2,5-disubstituted furans are obtained in moderate to good yields under mild reaction conditions. The scope of the reaction is quite decent, allowing for the synthesis of disubstituted furans having aryl and heteroaromatic groups.
- Mondal, Keshab,Pan, Subhas Chandra
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p. 4415 - 4421
(2017/04/27)
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- Ligand-, base-, co-catalyst-free copper fluorapatite (CuFAP) as a versatile, ecofriendly, heterogeneous and reusable catalyst for an efficient homocoupling of arylboronic acid at ambient reaction conditions
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This paper describes the first report in which copper species containing copper fluorapatite (CuFAP) acts as a versatile, eco-friendly, recyclable, heterogeneous catalyst for an efficient synthesis of symmetric biaryls from the homo-coupling of arylboronic acids in methanol solvent at ambient reaction conditions. The developed protocol is ligand-, base-, and co-catalyst-free, sustainable, mild, inexpensive, and compatible with a wide range of aromatic/heterocyclic boronic acids and provides the corresponding products in excellent yields without purification. The catalyst was easily recovered from the reaction mixture and reused several times without loss of activity.
- Mulla, Shafeek A. R.,Chavan, Santosh S.,Pathan, Mohsinkhan Y.,Inamdar, Suleman M.,Shaikh, Taufeekaslam M. Y.
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p. 24675 - 24680
(2015/03/30)
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- Bifurans via palladium-catalyzed Suzuki coupling
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Sixteen 2,2'-bifurans with aryl substituents are reported. The copper-mediated oxidative coupling of lithium salt of furan led to the formation of 2,2'-bifuran, which was brominated with either 2 eq. or 4 eq. NBS to afford 5,5'-dibromo-2,2'-bifuran and 3,3',5,5'-tetrabromo-2,2'-bifuran. The palladiumcatalyzed Suzuki reactions between dibromo or tetrabormo-bifuran and arylboronic acid were employed to furnish the title compounds, which were characterized by NMR spectra and mass spectra.
- Zhang, Jun,Ye, Peijun,He, Lu,Yuan, Ting,Liu, Qiancai
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p. 2190 - 2196
(2015/12/12)
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- Poly(mono-, bi- or trifuran): Effect of oligomer chain length on the electropolymerization performances and polymer properties
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Most recently, oligo-/polyfurans have regained widely attention due to their unique properties and promising applications in organic electronics. Herein, to acquire a thorough fundamental understanding of the electrosynthesis and properties of polyfuran (PFu) from different initial oligomers, the synthesis, fluorescence, and electropolymerization performances of α-oligofurans, namely furan (Fu), bifuran (2Fu), trifuran (3Fu), were comprehensively reported and the effect of oligomer chain length on the structure and properties of the resulting PFu films were evaluated. The oligofurans introduced here revealed higher fluorescence efficiency (0.05 for Fu, 0.19 for 2Fu and 0.27 for 3Fu) than the corresponding oligothiophenes and oligoselenophenes. The onset oxidation potential of oligofurans decreased obviously (1.25 V for Fu, 0.8 V for 2Fu, and 0.7 V for 3Fu) with the chain length of the starting monomers increasing, thus leading to the electrodeposition of high quality free-standing PFu films with improved optoelectronic properties. Structure characterization and properties of the as-formed PFu from different initial oligomers, including FT-IR, UV-vis, surface morphology, fluorescence, electroactivity and stability, electrochromic properties, etc., were systematically investigated and comprehensively discussed.
- Zhen, Shijie,Lu, Baoyang,Xu, Jingkun,Zhang, Shimin,Li, Yuzhen
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p. 14001 - 14012
(2014/04/17)
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- Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: A non-product specific route to C-8 substituted analogues
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Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO4 oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.
- Berezin, Andrey A.,Koutentis, Panayiotis A.
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experimental part
p. 4069 - 4078
(2011/06/24)
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- Deprotonative metalation of substituted benzenes and heteroaromatics using amino/alkyl mixed lithium-zinc combinations
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Different homoleptic and heteroleptic lithium-zinc combinations were prepared, and structural elements obtained on the basis of NMR spectroscopic experiments and DFT calculations. In light of their ability to metalate anisole, pathways were proposed to justify the synergy observed for some mixtures. The best basic mixtures were obtained either by combining ZnCl 2·TMEDA (TMEDA = N,N,N',N'tetramethylethylenediamine) with [Li(tmp)] (tmp = 2,2,6,6-tetramethylpiperidino; 3 equiv) or by replacing one of the tmp in the precedent mixture with an alkyl group. The reactivity of the aromatic lithium zincates supposedly formed was next studied, and proved to be substrate-, base-, and electrophile-dependent. The aromatic lithium zincates were finally involved in palladium-catalyzed cross-coupling reactions with aromatic chlorides and bromides.
- Snegaroff, Katia,Komagawa, Shinsuke,Chevallier, Floris,Gros, Philippe C.,Golhen, Stephane,Roisnel, Thierry,Uchiyama, Masanobu,Mongin, Florence
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experimental part
p. 8191 - 8201
(2010/09/11)
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- Efficient one-pot synthesis of 2-substituted furans from 3,3-diethoxypropyne and aldehydes using a Ti(O-i-Pr)4/2i-PrMgCl reagent
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A new, efficient and direct synthetic method for synthesizing 2-substituted furans using titanium-alkyne complex from easily preparable lithium propargyl alcohol derivatives derived from commercially available 3,3-diethoxypropyne, n-butyllithium and aldehydes by a Ti(O-i-Pr)4/2 i-PrMgCl reagent in 68-85percent yields.
- Eom, Deok Ki,Choi, Seong Jib,An, Duk Keun
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p. 1141 - 1146
(2008/02/08)
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- Gold(III) porphyrin-catalyzed cycloisomerization of allenones
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Gold(III) porphyrin-catalyzed cycloisomerization of allenones gave the corresponding furans in good to excellent yields (up to 98%) and with quantitative substrate conversions. By recovering the Au(III) catalyst, a recyclable catalytic system is developed with over 8300 product turnovers attained for the cycloisomerization of 1-phenyl-buta-2,3-dien-1-one. The versatility of the gold(III) porphyrin catalyst was exemplified by its application to the hydroamination and hydration of phenylacetylene in 73% and 87% yield, respectively.
- Zhou, Cong-Ying,Chan, Philip Wai Hong,Che, Chi-Ming
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p. 325 - 328
(2007/10/03)
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- A metathesis approach to aromatic heterocycles
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The ring closing metathesis (RCM) reaction can be used to prepare substituted furans and pyrroles. By utilising a Pd-catalysed coupling reaction with methoxyallene, allylic alcohols and sulfonamides can be converted into substrates that are ideal precursors to ring closing metathesis. After the RCM reaction is complete, the addition of acid promotes an elimination of methanol to form the fully aromatised system. A range of different substitution patterns and functional groups are compatible with this sequence. Double allene coupling, RCM and elimination reactions are also possible and allow the formation of biaryl systems. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
- Donohoe, Timothy J.,Orr, Allan J.,Gosby, Katherine,Bingham, Matilda
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p. 1969 - 1971
(2007/10/03)
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- Mild and efficient formation of symmetric biaryls via Pd(II) catalysts and Cu(II) oxidants
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Described herein is a mild and efficient palladium-catalyzed synthesis of symmetric biaryls from organostannanes. This methodology offers products rapidly in very high yields.
- Parrish, Jay P.,Flanders, Vincent L.,Floyd, Ryan J.,Jung, Kyung Woon
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p. 7729 - 7731
(2007/10/03)
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- Reductive coupling of halogenothiophenes and halogenothiazoles catalysed by PdII in a basic alcohol medium
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A catalytic reductive coupling method has been developed whereby 2- and 3-bromo- and 2-iodothiophenes, 2-bromothiazole and 2-bromofuran are converted into their corresponding bithiophene, bithiazole and bifuran derivatives. The use of a basic alcohol medium favours the reductive coupling pathway over the hydrodehalogenation pathway, which is generally more facile when other reducing agents are used. The catalytic mechanisms are discussed. The syntheses and characterization of the proposed intermediate complexes, trans-[PdBr(C4H3S-C)(PPh3)2] 1, trans-[PdI(C4H3S-C)(PPh3)2] 2 and trans-(N,P)-[{PdBr(μ-C3H2NS-C2,N)(PPh 3)}2]·1/2CHCl3 3 support the proposed mechanism and the catalytic results. Single-crystal X-ray crystallographic structure determinations of 2 and 3 were carried out.
- Xie, Yang,Tan, Geok Kheng,Yan, Yaw Kai,Vittal, Jagadese J.,Ng, Siu Choon,Hor, T. S. Andy
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p. 773 - 779
(2007/10/03)
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- Copper- and manganese-catalyzed homocoupling of organostannanes in the presence of iodine
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The copper- and manganese-catalyzed homocoupling of aryl-, alkenyl-, and alkynylstannanes to afford biaryls, 1,3-dienes, and 1,3-diynes were achieved in the presence of iodine at 100 °C in good yields.
- Kang, Suk-Ku,Baik, Tae-Gon,Jiao, Xiang Hua,Lee, Yong-Tack
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p. 2383 - 2384
(2007/10/03)
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- Palladium-catalyzed homocoupling of organostannanes
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A convenient method for palladium-catalyzed homocoupling of aryl-, vinyl-, and alkynylstannanes in dichloroethane in the presence of triphenylarsine under mild conditions is described.
- Kang, Suk-Ku,Namkoong, Eun-Young,Yamaguchi, Tokutaro
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p. 641 - 646
(2007/10/03)
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- Palladium Complexes Containing Rigid Bidentate Nitrogen Ligands as Catalysts for Carbon-Carbon Bond Formation
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Zerovalent Pd(Ar-BIAN)(dimethyl fumarate) and divalent PdCl2(Ar-BIAN) complexes containing the rigid bidentate nitrogen ligand bis(arylimino)acenaphthene (Ar-BIAN; Ar = C6H5, p-MeC6H4, p-MeOC6H4) are efficient catalysts for the cross coupling reaction of various organic halides (including acyl-, allyl-, aryl-, benzyl-, vinyl- and 1,2-dienylhalides) with organomagnesium, -zinc and -tin reagents.Coupling reactions of organic halides with one equivalent of organomagnesium and -zinc reagents, in the presence of 1 mol percent of a Pd(Ar-BIAN) catalyst, generally proceed smoothly in THF at 20 degC, giving complete conversion of the starting halide within 1-16 hours.Good isolated yields of carbon-carbon coupled products are obtained and the ratio cross/homo coupling varies between 98/2 and 0/100, depending on the substrates used.Reactions employing organotin reagents proceed best in DMF or HMPA and need longer reaction times and/or higher temperatures, as compared to organomagnesium and -zinc reagents, to go to completion.The selectivity for cross coupling is high (generally >99 percent) and high isolated yields of cross coupled products can be obtained.In the presence of carbon monoxide (1-5 bar) ketones can be formed with excellent selectivity and in good yields, as was demonstrated for the carbonylative coupling of benzyl bromide with tetramethyltin or (p-tolyl)trimethyltin.Comparison of some Pd(Ar-BIAN) catalyzed reactions with Pd-phosphine catalyzed reactions reveals that these reactions complement each other: for example, when a Pd(Ar-BIAN) catalyst was employed, the coupling of 2-methylallyl chloride with phenyltributyltin was much faster, whereas the coupling of iodobenzene with vinyltrimethyltin was much slower, as compared to the Pd(PPh3)n catalyzed reactions.
- Asselt, Rob van,Elsevier, Cornelis J.
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p. 323 - 334
(2007/10/02)
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- A Convenient Synthetic Route to bis-Heteroaromatic and bis-Heterocyclic Compounds Promoted by Liganded Nickel Complex Reducing Agents.
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A number of nitrogen, sulfur or oxygen containing bis-heteroaromatic or bis-heterocyclic derivatives have been synthesized in good to excellent yields by homocoupling of the corresponding halogenated compounds in the presence of liganded (triphenylphosphine or 2,2'-bipyridine) nickel Complex Reducing Agents in THF or DME at 63 deg C.
- Forst, Yves,Becker, Sandrine,Caubere, Paul
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p. 11893 - 11902
(2007/10/02)
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- Inter- and Intramolecular Biaryl Couplings Via Cyanocuprate Intermediates
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Low temperature oxidations of selected higher order cyanocuprates composed of one or two heteroaromatic ligands can be oxidatively coupled in an inter- or intramolecular fashion to afford unsymmetrical biaryls.Non-heteroaromatic systems have also been studied in related intramolecular processes.
- Lipshutz, Bruce H.,Kayser, Frank,Maullin, Nathalie
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p. 815 - 818
(2007/10/02)
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- New Synthetic Routes to Furans and Dihydrofurans from 1-Propargylbenzotriazole
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Base-assisted cyclizations of 1-propargyl>benzotriazoles, derived from lithiated 1-propargylbenzotriazole (1) and aromatic aldehydes or ketones, gave 2-arylfurans 5 or 1-(5,5-diaryl-2,5-dihydrofuran-2-yl)benzotriazoles 7, respectively, in high yields.Compounds 7 with Grignard reagents yielded trisubstituted 2,5-dihydrofurans 9.
- Katritzky, Alan R.,Li, Jianqing,Gordeev, Mikhail F.
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p. 3038 - 3041
(2007/10/02)
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- Method for preparing biaryl compounds
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An improved method for making biaryl compounds is disclosed, in which an aromatic acid halide having at least one strong electron-withdrawing group attached to or within the aromatic ring is reacted with at least one polysilane in the presence of an effective amount of a transition metal catalyst.
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- Palladium-Catalyzed Reductive Coupling of Aromatic Acid Dichlorides with Disilanes
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Electron-deficient aromatic acid-chlorides are converted to biphenyl compounds by palladium-catalyzed reaction with disilanes.
- Krafft, Terry E.,Rich, Jonathan D.,McDermott, Philip J.
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p. 5430 - 5432
(2007/10/02)
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- Nickel-Catalyzed Synthesis of Arylacetonitriles from Arylzinc Chlorides and Bromoacetonitrile
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Arylacetonitriles are synthesised by coupling arylzinc chlorides with bromoacetonitrile using Ni(acac)2/P(c-C6H11)(C6H5)2 as catalyst.The arylacetonitriles are reduced in situ with LiAlH4/AlCl3 to give the corresponding 2-aryl-1-aminoethanes.
- Frejd, Torbjoern,Klingstedt, Tomas
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- Synthesis of Biheteroaromatic Compounds via the Isoxazoline Route
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A number of heteroaromatically substituted furans, thiophenes, pyrroles, pyridines and benzenes have been prepared via the 2-isoxazoline route.N-Acetylnornicotyrine is prepared from N-allylacetamide and 3-pyridinecarboxaldoxime.
- Ghabrial, Sami S.,Thomsen, I.,Torssell, K. B. G.
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p. 426 - 434
(2007/10/02)
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- UNSYMMETRICAL HETEROBIARYL SYNTHESIS. A HIGHLY EFFICIENT PALLADIUM-CATALYZED CROSS-COUPLING REACTION OF HETEROARYL TRIALKYLSTANNANES WITH ARYL HALIDES
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A general synthesis of heterobiaryls in good yields via Pd-catalyzed cross-coupling of trialkylheteroarylstannanes 1-5 with aryl halides is described.
- Bailey, Thomas R.
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p. 4407 - 4410
(2007/10/02)
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- Uebergangsmetallaktivierte organische Verbindungen, IX. Synthese von Polyfuranen durch metallorganische oxidative Kupplung
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2,2'- (2a) and 3,3'-bifuran (3), hitherto only accessible by ring-forming syntheses in small yields, and the unknown compounds all-α-terfuran (2b) and all-α-quaterfuran (2c) have been prepared by convenient ring-connecting syntheses in 85, 46, 16, or 53percent-yield, respectively.Lithiation of 2a and subsequent reacting with iodine afforded 5-iodo-2,2'-bifuran (6b, 46percent).According to competition experiments acidity against n-butyllithium is increasing in the sequence furan 2a 2b.
- Kauffmann, Thomas,Lexy, Herbert,Kriegesmann, Reinhard
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p. 3667 - 3673
(2007/10/02)
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