- CIDNP 1H study of the photolysis of 7-sila- and 7-germa-norbornadienes
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The photochemical decomposition of 7-sila- and 7-germa-norbornadienes (1a,b) was studied by the CIDNP 1H technique.The reactions proceeds by a two-step mechanism via the reversible formation of singlet biradicals, II.The triplet biradical (II), formed as a result of S-T conversion of (II)(S), irreversibly decomposes giving Me2E (E = Si, Ge).The insertion of Me2E into the C-Br bond of PhCH2Br and the Sn-Cl bond of Me3SnCl occurs via a radical mechanism, as deduced from the CIDNP effects observed in these reactions.
- Kolesnikov, S. P.,Egorov, M. P.,Galminas, A. M.,Ezhova, M. B.,Nefedov, O. M.,et al.
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- SELF-REACTION OF PENTAMETHYLDISILYL RADICALS: IS DIMETHYLSILYLENE A PRODUCT?
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The self-reaction of the pentamethyldisilyl radical was investigated, in solution, at 298 deg K.Products due to the disproportionation and combination of these radicals were detected in a ratio /=0.48.However, there was no evidence for silylene formation.These results suggest that silylenes, which are formed during polysilane photolysis, are not produced from the self-reaction of polysilyl radicals but must be photo-extruded from the polysilane itself.
- Hawari, J. A.,Griller, D.,Weber, W. P.,Gaspar, P. P.
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- Paramagnetic intermediates in the photolysis of 7-silanorbornadiene studied by means of spin chemistry method
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The influence of an external magnetic field on the yield of photo-decomposition products of 7,7′-dimethyl-7-silanorbornadiene derivative has been detected in laser pulse photolysis experiments. The observations of magnetic field effects alterations in the presence of scavengers, O2 and PPh3, in combination with 1H-CIDNP data form the basis for the identification of the structure of paramagnetic intermediates involved in the process. It has been shown that magnetic field effects originate in biradical intermediates. These species result from both endocyclic Si-C bond cleavage in the initial compound and the reaction of dimethylsilylene (in a singlet or a triplet excited state) with starting 7-silanorbornadiene. To explain the influence of O2 upon the magnetic field effects, the reversible formation of oxygen complex with biradical species has been suggested.
- Taraban,Volkova,Kruppa,Plyusnin,Grivin,Ivanov, Yu.V.,Leshina,Egorov,Nefedov
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- Iodide [(η5-indenyl)IrI2]n: an effective precursor to (indenyl)iridium sandwich complexes
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The reactions of [(η5-indenyl)IrI2]η with CpTl or arenes in the presence of AgBF4 afford [(η5-indenyl)IrCp]+ or [(η5-indenyl)Ir(arene)]2+ cations (arene = benzene, mes
- Chamkin, Alexander A.,Finogenova, Anastasiia M.,Nelyubina, Yulia V.,Laskova, Julia,Kudinov, Alexander R.,Loginov, Dmitry A.
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- Iridium-catalyzed reaction of aroyl chlorides with internal alkynes to produce substituted naphthalenes and anthracenes
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Benzoyl chlorides efficiently react with 2 equiv of dialkylacetylenes as well as diphenylacetylene in the presence of an iridium catalyst accompanied by decarbonylation to produce 1,2,3,4-tetrasubstituted naphthalenes in good yields. Use of 2-naphthoyl ch
- Yasukawa, Toshiya,Satoh, Tetsuya,Miura, Masahiro,Nomura, Masakatsu
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- Synthesis of tetrasubstituted naphthalenes by palladium-catalyzed reaction of aryl iodides with internal alkynes
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The 1:2 coupling of aryl iodides with acetylene-dicarboxylate esters and diphenylacetylene efficiently proceeds in the presence of a palladium catalyst with use of silver carbonate as base to produce the corresponding tetrasubstituted naphthalenes.
- Kawasaki, Satoshi,Satoh, Tetsuya,Miura, Masahiro,Nomura, Masakatsu
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- Attempts to observe spin catalysis by paramagnetic particles in the photolysis of 7-silanorbonadiene in solution
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Addition of the stable radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4-OH-TEMPO), to the reaction mixture in the photolysis of 7-silanorbornadiene in solution results in the decrease of the magnetic field effect detected for the yield of stable
- Volkova, Olga S.,Taraban, Marc B.,Plyusnin, Victor F.,Leshina, Tatyana V.,Egorov, Michael P.,Nefedov, Oleg M.
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Read Online
- Formation of a Naphthalene Framework by Rhodium(III)-Catalyzed Double C-H Functionalization of Arenes with Alkynes: Impact of a Supporting Ligand and an Acid Additive
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An efficient protocol has been developed for the synthesis of larger condensed arenes from aromatic hydrocarbons and internal alkynes. This protocol uses readily available [CpRhI2]nas a catalyst and Cu(OAc)2as an oxidant and proceeds smoothly through undirected double C-H activation. The addition of trifluoroacetic acid has a crucial positive impact on the reaction selectivity and the yields of the target products. In contrast to the previously reported catalytic systems, the new conditions allow the use of both dialkyl- and diarylacetylenes with the same high efficiency.
- Kharitonov, Vladimir B.,Loginov, Dmitry A.,Muratov, Dmitry V.,Nelyubina, Yulia V.
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- CO2-activated NaClO-5H2O enabled smooth oxygen transfer to iodoarene: A highly practical synthesis of iodosylarene
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A safe, rapid, and environmentally friendly synthesis of iodosylarene (ArIO) has been developed using NaClO under a carbon dioxide (CO2) atmosphere. Exposure of iodoarene to NaClO-5H2O in acetonitrile under CO2 (1 atm) resulted in the clean formation of ArIO within 10 minutes in high yield. The absence of a base in this method enables the direct use of in-situ-generated iodosylarene not only for a variety of oxidative transformations (synthesis of sulfilimine, pentavalent bismuth, benzyne adduct, etc.), but also for the synthesis of iodonium ylide and imino-λ3-iodane in one pot.
- Miyamoto, Kazunori,Watanabe, Yuichiro,Takagi, Taisei,Okada, Tomohide,Toyama, Takashi,Imamura, Shinji,Uchiyama, Masanobu
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- Synthesis of Benzo-Fused Cyclic Compounds via Rhodium-Catalyzed Decarboxylative Coupling of Aromatic Carboxylic Acids with Alkynes
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The decarboxylative coupling of diversely substituted benzoic acids with internal alkynes proceeds smoothly in the presence of a [RhCl(cod)] 2/1,2,3,4-tetraphenyl-1,3-cyclopentadiene catalyst system to selectively produce highly substituted nap
- Inai, Yasuhito,Usuki, Yoshinosuke,Satoh, Tetsuya
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supporting information
p. 3029 - 3036
(2021/04/15)
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- Synthesis of Overloaded Cyclopentadienyl Rhodium(III) Complexes via Cyclotetramerization of tert-Butylacetylene
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Herein we describe the synthesis and reactivity of rhodium catalysts with the very bulky cyclopentadienyl ligand C8H3tBu4 (designated as tBu4Cp). The reaction of [Rh(cod)Cl]2 with tert-butylacetylene in the presence of Et3N gives the complex (tBu4Cp)Rh(cod) (60-65% yield), in which the cyclopentadienyl ligand tBu4Cp is assembled from four alkyne molecules. The oxidation of (tBu4Cp)Rh(cod) with chlorine or bromine gives the corresponding halide complexes (tBu4Cp)RhX2 (X = Cl (85%), Br (95%)), which have unusual 16-electron monomeric structures due to the steric shielding provided by tBu groups. A similar reaction with iodine gives the ionic dinuclear complex [(tBu4Cp)RhI3Rh(tBu4Cp)]I (99%) with halide bridges. The bromide complex (tBu4Cp)RhBr2 reacts with phosphorus ligands such as P(OMe)3, P(OPh)3, PMe2Ph, and PMePh2 to give the 18-electron adducts (tBu4Cp)RhBr2(PR3), but no reaction occurs with larger phosphines such as PPh3. The racemic chloride (tBu4Cp)RhCl2 can be separated into enantiomers by preparative TLC of its diastereomeric adducts with (R)-phenylglycinol. The complex (tBu4Cp)RhBr2 catalyzes C-H activation and annulation of O-pivaloyl-hydroxamate as well as insertion of phenyldiazoacetate into E-H bonds, although the reaction rates and the substrate scope are limited by the bulky tBu4Cp ligand.
- Kolos, Andrey V.,Nelyubina, Yulia V.,Perekalin, Dmitry S.,Sundararaju, Basker
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supporting information
p. 3712 - 3719
(2021/09/18)
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- Easy Access to Versatile Catalytic Systems for C?H Activation and Reductive Amination Based on Tetrahydrofluorenyl Rhodium(III) Complexes
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On the basis of the 1,2,3,4-tetrahydrofluorenyl ligand, a simple approach was developed to new effective rhodium catalysts for the construction of C?C and C?N bonds. The halide compounds [(η5-tetrahydrofluorenyl)RhX2]2 (2
- Kharitonov, Vladimir B.,Runikhina, Sofiya A.,Nelyubina, Yulia V.,Muratov, Dmitry V.,Chusov, Denis,Loginov, Dmitry A.
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supporting information
p. 10903 - 10912
(2021/06/28)
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- Trimethylammonium-containing rhodacarborane [(9-NMe3-7,8-C2B9H10)RhCl2]2 as a catalyst for the annulation of arylcarboxylic acids with alkynes
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Rhodacarborane [(9-NMe3-7,8-C2B9H10)RhCl2]2 exhibited moderate catalytic activity in the reaction of annulation of arylcarboxylic acids with alkynes, giving naphthalenes as the major produc
- Loginov, D. A.,Molotkov, A. P.,Timofeev, S. V.
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p. 1922 - 1926
(2021/11/04)
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- Catalytic Asymmetric Electrochemical α-Arylation of Cyclic β-Ketocarbonyls with Anodic Benzyne Intermediates
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Asymmetric catalysis with benzyne remains elusive because of the highly fleeting and nonpolar nature of benzyne intermediates. Reported herein is an electrochemical approach for the oxidative generation of benzynes (cyclohexyne) and its successful merging with chiral primary aminocatalysis, formulating the first catalytic asymmetric enamine–benzyne (cyclohexyne) coupling reaction. Cobalt acetate was identified to stabilize the in situ generated arynes and facilitate its coupling with an enamine. This catalytic enamine-benzyne protocol provides a concise method for the construction of diverse α-aryl (α-cyclohexenyl) quaternary carbon stereogenic centers with good stereoselectivities.
- Fu, Niankai,Li, Longji,Li, Yao,Luo, Sanzhong,Zhang, Long
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supporting information
p. 14347 - 14351
(2020/07/13)
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- Effect of Cp-Ligand Methylation on Rhodium(III)-Catalyzed Annulations of Aromatic Carboxylic Acids with Alkynes: Synthesis of Isocoumarins and PAHs for Organic Light-Emitting Devices
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An efficient protocol was developed for the synthesis of π-extended isocoumarins and polycyclic aromatic hydrocarbons based on the oxidative coupling of aromatic carboxylic acids with internal alkynes catalyzed by (cyclopentadienyl)rhodium complexes. The
- Molotkov, Alexander P.,Arsenov, Mikhail A.,Kapustin, Daniil A.,Muratov, Dmitry V.,Shepel', Nikolay E.,Fedorov, Yury V.,Smol'yakov, Alexander F.,Knyazeva, Elena I.,Lypenko, Dmitry A.,Dmitriev, Artem V.,Aleksandrov, Alexey E.,Maltsev, Eugeny I.,Loginov, Dmitry A.
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p. 334 - 345
(2020/03/10)
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- Tris(pyrazolyl)borate rhodium complexes. Application for reductive amination and esterification of aldehydes in the presence of carbon monoxide
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The halide complexes TpRhCl2(MeOH) and TpMe2RhI2(CO) (Tp = hydrotris-(pyrazolyl)borate; TpMe2 = hydrotris-(3,5-dimethylpyrazolyl)borate) were synthesized by reactions of RhCl3 with K[Tp] in methanol and TpMe2Rh(CO)2 with iodine, respectively. Reactions of TpMe2RhCl2(MeOH) and TpMe2RhI2(CO) with 1,10-phenanthroline afford the phenanthroline derivatives [TpMe2Rh(phen)X]+ (X = Cl, I). The structures of TpRhCl2(MeOH) and TpRhI2(CO) were determined by X-ray diffraction. Tris(pyrazolyl)borate rhodium complexes effectively catalyze the reductive amination and the reductive esterification of aldehydes in the presence of carbon monoxide.
- Kharitonov, Vladimir B.,Ostrovskii, Vladimir S.,Nelyubina, Yulia V.,Muratov, Dmitry V.,Chusov, Denis,Loginov, Dmitry A.
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- Group 4 Diarylmetallocenes as Bespoke Aryne Precursors for Titanium-Catalyzed [2 + 2 + 2] Cycloaddition of Arynes and Alkynes
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Despite the ubiquity of reports describing titanium (Ti)-catalyzed [2 + 2 + 2] cyclotrimerization of alkynes, the incorporation of arynes into this potent manifold has never been reported. The in situ generation of arynes often requires fluoride, which instead will react with the highly fluorophilic Ti center, suppressing productive catalysis. Herein, we describe the use of group 4 diarylmetallocenes, CpR2MAr2 (CpR = C5H5, C5Me5; M = Ti, Zr), as aryne precursors for the Ti-catalyzed synthesis of substituted naphthalenes via coupling with 2 equiv of an alkyne. Fair-to-good yields of the desired naphthalene products could be obtained with 1% catalyst loadings, which is roughly an order of magnitude lower than similar reactions catalyzed by palladium or nickel. Additionally, naphthalenes find broad applications in the electronics, photovoltaics, and pharmaceutical industries, urging the discovery of more economic syntheses. These results indicate that aryne transfer from a CpR2M(?2-aryne) complex to another metal is a viable route for the introduction of aryne fragments into organometallic catalytic processes.
- Reiner, Benjamin R.,Tonks, Ian A.
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supporting information
p. 10508 - 10515
(2019/09/13)
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- Rhodaelectrocatalysis for Annulative C?H Activation: Polycyclic Aromatic Hydrocarbons through Versatile Double Electrocatalysis
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Rapid access to structurally diversified polycyclic aromatic hydrocarbons (PAHs) in a controlled manner is of key significance in materials sciences. Herein, we describe a strategy featuring two distinct electrocatalytic C?H transformations for the synthesis of novel nonplanar PAHs. The combination of rhodaelectrooxidative C?H activation/[2+2+2] alkyne annulation of easily accessible boronic acids with electrocatalytic cyclodehydrogenation provided modular access to diversely substituted PAHs with electricity as a sustainable oxidant. The unique molecular topology as well as the photophysical and electronic properties of the thus obtained PAHs were fully analyzed. The unique power of this metallaelectrocatalysis method was demonstrated by the chemoselective assembly of synthetically useful iodo-substituted PAHs.
- Kong, Wei-Jun,Finger, Lars H.,Oliveira, Jo?o C. A.,Ackermann, Lutz
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supporting information
p. 6342 - 6346
(2019/04/08)
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- Polyaromatic Products of Three-Component Coupling of Aryl Halide with Two Molecules of Arylacetylene and Arylboronic Acid under Ligand-Free Catalysis Conditions
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The aryl halide-arylacetylene-arylboronic acid three-component coupling in the presence of a Pd catalyst containing no organic ligands is described. The reaction routes that take place in the reaction system are shown to include the consecutive carbopalla
- Yarosh,Larina,Lagoda,Kurokhtina,Schmidt
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p. 678 - 681
(2019/07/15)
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- Generation of arynes by selective cleavage of a carbonphosphorus bond of o-(diarylphosphinyl)aryl triflates using a grignard reagent
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A novel method for generating arynes, including disubsti-tuted benzynes and a dehydrophenoxathiin, is reported. The treatment of easily synthesizable o-(diarylphosphinyl)aryl triflates having two electron-deficient aromatic groups on the phosphorus atom with a phenyl Grignard reagent triggered the efficient generation of arynes by selective cleavage of a carbonphosphorus bond.
- Nishiyama, Yoshitake,Kamada, Shuhei,Yoshida, Suguru,Hosoya, Takamitsu
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p. 1216 - 1219
(2018/09/11)
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- Trisulfur Radical Anion (S3?-) Involved [1 + 2 + 2] and [1 + 3 + 1] Cycloaddition with Aromatic Alkynes: Synthesis of Tetraphenylthiophene and 2-Benzylidenetetrahydrothiophene Derivatives
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S3?--mediated [1 + 2 + 2] and [1 + 3 + 1] cycloaddition reactions of aromatic alkynes to give tetraphenylthiophene and 2-benzylidenetetrahydrothiophene derivatives via two C-S bond formations are developed. These two protocols provide new, simple, and straightforward strategies to construct tetraphenylthiophene and 2-benzylidenetetrahydrothiophene derivatives under transition-metal-free conditions. This study also expands the application of S3?- in organic reactions.
- Li, Jing-Hao,Huang, Qi,Wang, Shun-Yi,Ji, Shun-Jun
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supporting information
p. 4704 - 4708
(2018/08/07)
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- Room Temperature Decarboxylative and Oxidative [2+2+2] Annulation of Benzoic Acids with Alkynes Catalyzed by an Electron-Deficient Rhodium(III) Complex
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It has been established that an electron-deficient (η5-cyclopentadienyl)rhodium(III) [CpERhIII] complex is capable of catalyzing the decarboxylative and oxidative [2+2+2] annulation of benzoic acids with alkynes to produce substituted naphthalenes at room temperature. The appropriate choice of the additive and the solvent is crucial for this transformation. This catalyst system allowed use of oxygen as a terminal oxidant and broadened the substrate scope including both aromatic and aliphatic alkynes. In this catalysis, the electron deficient nature of the CpERhIII catalyst would cause the strong rhodium-π interaction, which accelerates the decarboxylation as well as the C?H bond cleavage.
- Honjo, Yusaku,Shibata, Yu,Kudo, Eiji,Namba, Tomoya,Masutomi, Koji,Tanaka, Ken
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supporting information
p. 317 - 321
(2017/11/01)
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- Cyclooctadiene iridium complexes [Cp*Ir(COD)X]+ (X = Cl, Br, I): Synthesis and application for oxidative coupling of benzoic acid with alkynes
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The cyclooctadiene iridium complexes [Cp*Ir(COD)X]PF6 ([1a?c]PF6; X = Cl, Br, I) were synthesized by reactions of Cp*Ir(COD) with halogens followed by a counterion exchange. The cyclooctadiene in these complexes is a thermally labile
- Datsenko, Vera P.,Nelyubina, Yulia V.,Smol'yakov, Alexander F.,Loginov, Dmitry A.
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- Computational Characterization of the Mechanism for the Oxidative Coupling of Benzoic Acid and Alkynes by Rhodium/Copper and Rhodium/Silver Systems
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DFT calculations were applied to study the oxidative coupling between benzoic acid and 1-phenyl-1-propyne catalyzed by [CpRhCl2]2 (Cp=cyclopentadienyl) by using either Cu(OAc)2(H2O) or Ag(OAc) as the terminal ox
- Funes-Ardoiz, Ignacio,Maseras, Feliu
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p. 12383 - 12388
(2018/05/08)
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- Rhodium-catalyzed carbonylative annulation of 2-bromobenzylic alcohols with internal alkynes using furfural via β-aryl elimination
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In spite of the significant progress made in transformations of unstrained benzylic (tert-)alcohols through β-aryl elimination, catalytic carbonylation has not yet been developed extensively because alkoxycarbonylation is probably favored over β-aryl elim
- Furusawa, Takuma,Tanimoto, Hiroki,Nishiyama, Yasuhiro,Morimoto, Tsumoru,Kakiuchi, Kiyomi
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supporting information
p. 926 - 929
(2017/06/27)
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- μ-Borole triple-decker complexes as catalysts for oxidative coupling of benzoic acid with alkynes. Structure of a hybrid rhodacyclopentadienyl/borole triple-decker complex
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Reaction of dimethylamine adduct of 1-methyl-3-borolene with [(C2H4)2RhCl]2 gives the triple-decker complex (η-C4H4BMe)Rh(μ-η:η-C4H4BMe)Rh(η-C4H4
- Loginov, Dmitry A.,Muratov, Dmitry V.,Nelyubina, Yulia V.,Laskova, Julia,Kudinov, Alexander R.
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p. 393 - 397
(2016/12/16)
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- Cationic iridacarboranes [3-(arene)-3,1,2-IrC2B9H11]+ and [3-(MeCN)3-3,1,2-IrC2B9H11]+: Synthesis, reactivity, and bonding. Catalysis of oxidative coupling
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(Arene)iridacarboranes [3-(arene)-3,1,2-IrC2B9H11]+ (arene = benzene (1a), toluene (1b), o-xylene (1c), m-xylene (1d), durene (1e)) were synthesized by reaction of [(cod)IrCl]2 with Tl[Tl(η-7,8-C
- Loginov, Dmitry A.,Belova, Alena O.,Vologzhanina, Anna V.,Kudinov, Alexander R.
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p. 232 - 240
(2015/03/30)
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- Generation of arynes triggered by sulfoxidemetal exchange reaction of ortho-sulfinylaryl triflates
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Arynes were efficiently generated from readily available ortho-sulfinylaryl triflates by the treatment with phenylmagnesium bromide in tetrahydrofuran at 78 C. Aryne generation was initiated by a rapid sulfoxidemetal exchange reaction, followed by the immediate elimination of the ortho-OTf group. Various arynophiles efficiently reacted with arynes generated by this method within 10min, providing the corresponding adducts in high yields.
- Yoshida, Suguru,Uchida, Keisuke,Hosoya, Takamitsu
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p. 116 - 118
(2014/01/23)
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- Rhodacarboranes as catalysts for oxidative coupling of benzoic acid with diphenylacetylene
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Rhodacarboranes [(9-SMe2-7,8-Me2-C2B9H8)RhCl2]2, [(1-ButNH-1,7,9-C3B8H10)-RhI2]2, [(9-SMe2-7,8-C
- Loginov,Belova,Kudinov
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p. 983 - 986
(2015/02/05)
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- Three-bond breaking of cyclic anhydrides: Easy access to polyfunctionalized naphthalenes and phenanthrenes
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Benzannulation of phthalic anhydrides with alkynes to polyfunctionalized naphthalenes and phenanthrenes was confirmed to be straightforward using a palladium catalytic system. Sequential liberation of CO2 and CO occurred via oxidative decomposition of anhydride. In the case of 1,8-naphthalenedicarboxylic anhydrides, both aryls were encompassed in the annulation reaction to afford acenaphthylenes.
- Jafarpour, Farnaz,Hazrati, Hamideh,Nouraldinmousa, Sorour
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supporting information
p. 3816 - 3819
(2013/09/02)
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- Solvent free, phosphine free Pd-catalyzed annulations of aryl bromides with diarylacetylenes
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Palladium nanoparticles and sodium acetate catalyze the reaction of aryl bromide with diarylacetylene to produce annulated products in good yield. One equivalent of PEG-600 serves as the solvent. This procedure is compatible with a wide variety of functional groups.
- Bej, Ansuman,Chakraborty, Amarnath,Sarkar, Amitabha
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p. 15812 - 15819
(2013/09/12)
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- Synthesis of polysubstituted naphthalenes by iron-catalyzed [2+2+2] annulation of grignard reagents with alkynes
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Iron catalyzes the oxidative [2+2+2] annulation of an arylmagnesium compound with two molecules of an internal alkyne via C-H bond activation at 0 °C to produce polysubstituted naphthalene. Georg Thieme Verlag Stuttgart.New York.
- Ilies, Laurean,Matsumoto, Arimasa,Kobayashi, Motoaki,Yoshikai, Naohiko,Nakamura, Eiichi
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supporting information
p. 2381 - 2384
(2013/07/19)
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- Bromine-mediated cyclization of 1,4-diaryl buta-1,3-diyne to 1,2,3-tribromo-4-aryl naphthalene
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Bromine-mediated intramolecular cyclization of 1,4-diaryl buta-1,3-diynes has been developed for the construction of naphthalene motifs. A number of 1,2,3-tribromo-4-aryl naphthalenes are synthesized under mild reaction condition by the 6-endo-dig electro
- Singha, Raju,Nandi, Sukla,Ray, Jayanta K.
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supporting information
p. 6531 - 6534,4
(2012/12/11)
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- Bromine-mediated cyclization of 1,4-diaryl buta-1,3-diyne to 1,2,3-tribromo-4-aryl naphthalene
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Bromine-mediated intramolecular cyclization of 1,4-diaryl buta-1,3-diynes has been developed for the construction of naphthalene motifs. A number of 1,2,3-tribromo-4-aryl naphthalenes are synthesized under mild reaction condition by the 6-endo-dig electro
- Singha, Raju,Nandi, Sukla,Ray, Jayanta K.
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supporting information
p. 6531 - 6534
(2013/01/15)
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- Iron-catalyzed annulation reaction of arylindium reagents and alkynes to produce substituted naphthalenes
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We report here an iron-bisphosphine complex-catalyzed annulation reaction of an arylindium reagent and two alkyne molecules that affords a substituted naphthalene derivative in moderate to good yield. The reaction represents a new example of iron-catalyzed C-C bond forming reactions via C-H bond functionalization.
- Adak, Laksmikanta,Yoshikai, Naohiko
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experimental part
p. 5167 - 5171
(2012/07/31)
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- Synthesis of highly substituted acenes through rhodium-catalyzed oxidative coupling of arylboron reagents with alkynes
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The rhodium-catalyzed oxidative 1:2 coupling reactions of arylboronic acids or their esters with alkynes smoothly proceed to produce the corresponding annulated products. Of special note, highly substituted, readily soluble, and tractable anthracene and tetracene derivatives can be obtained selectively from 2-naphthyl- and 2-anthrylboron reagents, respectively.
- Fukutani, Tatsuya,Hirano, Koji,Satoh, Tetsuya,Miura, Masahiro
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experimental part
p. 2867 - 2874
(2011/05/28)
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- Synthesis of 1,4-diarylbuta-1,3-dienes through palladium-catalyzed decarboxylative coupling of unsaturated carboxylic acids
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It has been found that readily available hydroxylated cinnamic acids such as ferulic acid undergo palladium-catalyzed decarboxylative coupling with aryl iodides and internal alkynes in a 1:1:1 manner to produce 1,4-diarylbuta-1,3- dienes. The butadiene synthesis has also been achieved through the coupling of aryl halides with dienoic acids. Some of the products exhibit solid-state fluorescence.
- Yamashita, Mana,Hirano, Koji,Satoh, Tetsuya,Miura, Masahiro
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experimental part
p. 631 - 636
(2011/04/26)
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- Generation of benzyne from benzoic acid using C-H activation
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ortho C-H activation of benzoic acids with Pd(ii) generates an oxapalladacycle that can decarboxylate to produce a palladium-associated aryne. The arynes then undergo [2+2+2] trimerisation to afford triphenylenes.
- Cant, Alastair A.,Roberts, Lee,Greaney, Michael F.
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supporting information; experimental part
p. 8671 - 8673
(2011/01/03)
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- Palladium-catalyzed three-component 1:2:1 coupling of aryl iodides, alkynes, and alkenes to produce 1,3,5-hexatriene derivatives
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The intermolecular three-component coupling of aryl iodides, diarylacetylenes, and alkenes effectively proceeds in the presence of palladium acetylacetonate and silver acetate as catalyst and base, respectively, to give the corresponding 1:2:1 coupling pr
- Horiguchi, Hakaru,Hirano, Koji,Satoh, Tetsuya,Miura, Masahiro
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supporting information; experimental part
p. 1431 - 1436
(2010/02/28)
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- Synthesis of highly substituted naphthalene and anthracene derivatives by rhodium-catalyzed oxidative coupling of arylboronic acids with alkynes
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The rhodium-catalyzed oxidative 1:2 coupling reactions of arylboronic acids with alkynes effectively proceeds in the presence of a copper-air oxidant to produce the corresponding annulated products. Of special note, anthracene derivatives can be obtained
- Fukutani, Tatsuya,Hirano, Koji,Satoh, Tetsuya,Miura, Masahiro
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supporting information; experimental part
p. 5198 - 5201
(2009/12/29)
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- Synthesis of silicon-functionalized 7-silanorbornadienes and their thermolysis and photolysis
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A series of 7-silanorbornadienes were prepared and characterized by X-ray crystallographic analysis. 2,3-Benzo-7-mesityl-1,4,5,6-tetraphenyl-7-silanorbornadiene (1a) was prepared by the [4+2] cycloaddition reaction of 1-mesityl-2,3,4,5-tetraphenyl-1-sila-
- Okimoto, Masahiro,Kawachi, Atsushi,Yamamoto, Yohsuke
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experimental part
p. 1419 - 1426
(2009/10/01)
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- Palladium-catalyzed formation of highly substituted naphthalenes from arene and alkyne hydrocarbons
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Several highly substituted naphthalenes 3 have been synthesized in a one-pot reaction by treatment of arenes 1 with alkynes 2 in the presence of palladium acetate and silver acetate. In this Pd-catalyzed protocol, an arene provides a benzo source for the construction of a naphthalene core through twofold aryl C - H bond activation. Reaction of triphenylphosphine with diphenylethyne (2 a) under the catalysis of PdIV complexes produced 1,2,3,4-tetraphenylnaphthalene (3ba) in 62% yield. Here, triphenylphosphine undergoes one aryl C - P bond cleavage and one aryl C - H bond activation to serve as a benzo moiety. Crystal structures of cycloadducts 3ea, 3ga, and 3ac have been analyzed. The twisted naphthalenes arise not only from the overcrowded substituents but also from the contribution of the CH3-π interaction.
- Wu, Yao-Ting,Huang, Ke-Hsin,Shin, Chien-Chueh,Wu, Tsun-Cheng
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experimental part
p. 6697 - 6703
(2009/07/01)
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- Synthesis, structure, and photophysical properties of highly substituted 8,8a-dihydrocyclopenta[a]indenes
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(Chemical Equation Presented) A triple round: A palladium-catalyzed cyclotrimerization of 1,2-diarylacetylenes has been developed to synthesize highly substituted 8,8a-dihydrocyclopenta[a]indenes. One such cycloadduct (1) displays unusual aggregation-induced emission with a strong blue fluorescence (see picture). The structures of the products have been confirmed by X-ray crystal analysis.
- Wu, Yao-Ting,Kuo, Ming-Yu,Chang, Yu-Ting,Shin, Chien-Chueh,Wu, Tsun-Cheng,Tai, Chia-Cheng,Cheng, Tzu-Heng,Liu, Wei-Szu
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scheme or table
p. 9891 - 9894
(2009/05/07)
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- Palladium-catalyzed three-component arylcyanation of internal alkynes with Aryl bromides and K4[Fe(CN)6]
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The one-pot, palladium-catalyzed, three-component coupling of aryl bromides, internal alkynes, and environmentally friendly K4[Fe(CN) 6] provides an efficient and direct method for the preparation of β-arylalkenylnitriles.
- Cheng, Yi-Nan,Duan, Zheng,Yu, Liujian,Li, Zhongxian,Zhu, Yu,Wu, Yangjie
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supporting information; experimental part
p. 901 - 904
(2009/04/07)
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- O-Dihaloarenes as aryne precursors for nickel-catalyzed [2 + 2 + 2] cycloaddition with alkynes and nitriles
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o-Dihaloarenes acting as aryne precursors react with acetylenes and nitriles catalyzed by the NiBr2(dppe)/dppe/Zn system to give substituted naphthalene, phenanthridine or triphenylene derivatives depending on the reaction conditions in moderat
- Hsieh, Jen-Chieh,Cheng, Chien-Hong
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supporting information; experimental part
p. 2992 - 2994
(2009/02/04)
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- Rhodium-catalyzed oxidative coupling of triarylmethanols with internal alkynes via successive C-H and C-C bond cleavages
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(Chemical Equation Presented) The rhodium-catalyzed oxidative coupling of triarylmethanols with internal alkynes effectively proceeds in a 1:2 manner via cleavage of C-H and C-C bonds to produce the corresponding naphthalene derivatives. Addition of trior tetraphenylcyclopentadiene as a ligand is crucial for the reaction to occur efficiently.
- Uto, Toshihiko,Shimizu, Masaki,Ueura, Kenji,Tsurugi, Hayato,Satoh, Tetsuya,Miura, Masahiro
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p. 298 - 300
(2008/09/17)
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- Rhodium- and iridium-catalyzed oxidative coupling of benzoic acids with alkynes via regioselective C-H bond cleavage
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(Chemical Equation Presented) The oxidative coupling of benzoic acids with internal alkynes effectively proceeds in the presence of [Cp*RhCl 2]2 and Cu(OAc)2·H2O as catalyst and oxidant, respectively, to produce
- Ueura, Kenji,Satoh, Tetsuya,Miura, Masahiro
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p. 5362 - 5367
(2008/02/08)
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- Rh(I)-catalyzed carbonylative cyclization reactions of alkynes with 2-bromophenylboronic acids leading to indenones
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The Rh-catalyzed reaction of alkynes with 2-bromophenylboronic acids involves carbonylative cyclization to give indenones. The key steps in the reaction involve the addition of an arylrhodium(I) species to an alkyne and the oxidative addition of C-Br bond
- Harada, Yasuyuki,Nakanishi, Jun,Fujihara, Hirokazu,Tobisu, Mamoru,Fukumoto, Yoshiya,Chatani, Naoto
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p. 5766 - 5771
(2008/02/04)
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- Improved solubility of hypervalent iodine-benzyne precursors: Synthesis and reaction of (phenyl)[2-(trimethylsilyl)phenyl]iodonium salts bearing long alkyl chains
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Synthesis of new long-chained hypervalent iodine-benzyne precursors, (4-dodecylphenyl)[2-(trimethylsilyl)phenyl]iodonium triflate and the tetradecyl derivative, is described. The benzyne precursors dissolve even in organic solvents of low polarity such as diethyl ether, THF, cyclopentyl methyl ether, benzene, and toluene. The trapping reactions with furan and tetraphenylcy-clopentadienone in the above solvent give the benzyne adducts in high yields without any loss of high reactivity of hypervalent iodine-benzyne precursors.
- Kitamura, Tsugio,Abe, Takayoshi,Fujiwara, Yuzo,Yamaji, Teizo
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p. 213 - 216
(2007/10/03)
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- Synthesis of a new hypervalent iodine compound, [2-(hydroxydimethylsilyl)phenyl](phenyl)iodonium triflate as a convenient approach to benzyne
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A new benzyne precursor, [2-(hydroxydimethylsilyl)phenyl](phenyl)iodonium triflate, is prepared from 1,2-dibromobenzene in good yield. This procedure avoids the use of carcinogenic HMPA and the severe reaction conditions. The reaction of the benzyne precursor with Bu4NF in the presence of a trapping agent under very mild conditions efficiently generates benzyne and gives the benzyne adduct in high yield. (C) 2000 Elsevier Science Ltd.
- Kitamura,Meng,Fujiwara
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p. 6611 - 6614
(2007/10/03)
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- Complexation of paramagnetic intermediates formed in the photolysis of 7,7-dimethyl-1,4,5,6-tetraphenyl-2,3-benzo-7-silanorbornadiene: A study by spin chemistry methods
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Complexation of paramagnetic intermediates formed in the photolysis of 7,7-dimethyl-1,4,5,6-tetraphenyl-2,3-benzo-7-silanorbornadiene with n-donors (PPh3, O2) was studied by spin chemistry methods.
- Leshina,Taraban,Plyusnin,Volkova,Egorov
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p. 421 - 426
(2007/10/03)
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- A new and efficient hypervalent iodine-benzyne precursor, (phenyl)[o- (trimethylsilyl)phenyl]iodonium triflate: Generation, trapping reaction, and nature of benzyne
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A new and efficient hypervalent iodine-benzyne precursor, (phenyl)[2- (trimethylsilyl)phenyl]-iodonium triflate (10), is reported. The hypervalent iodine-benzyne precursor 10 is readily prepared by reaction of 1,2- bis(trimethylsilyl)benzene with a PhI(OAc)2/TfOH reagent system. Treatment of 10 with Bu4NF in CH2Cl2 at room temperature gives high yields of the benzyne adducts in the presence of a trapping agent such as furan, 2- methylfuran, anthracene, tetraphenylcyclopentadienone, or 1,3- diphenylisobenzofuran. Especially, the result of the reaction in the presence of furan indicates a quantitative generation of benzyne and its efficient capture by the furan. Similarly, methylbenzynes (22 and 27) are efficiently generated from the corresponding methyl-substituted (trimethylsilyl)phenyliodonium triflates (12 and 13). The preparation of the hypervalent iodine-benzyne precursors, the generation of benzynes, the trapping reactions, and the nature are described in detail together with the advantages of the present reagents over the previously reported benzyne precursors.
- Kitamura, Tsugio,Yamane, Masakatsu,Inoue, Kensuke,Todaka, Mitsuru,Fukatsu, Norihiko,Meng, Zhaohong,Fujiwara, Yuzo
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p. 11674 - 11679
(2007/10/03)
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