- MIDA boronate allylation-synthesis of ibuprofen
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MIDA boronates are among the most useful reagents for the Suzuki-Miyaura reaction. This chemistry typically generates new bonds between two aromatic rings, thereby restricting access to important areas of chemical space. Here we demonstrate the coupling of MIDA boronates to allylic electrophiles, including a new synthesis of the well-known COX inhibitor ibuprofen. This journal is
- Brodie, Glen,France, David J.,Memarzadeh, Sarah,Phillips, David,Tang, Gi Lum
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p. 30624 - 30630
(2020/09/11)
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- Photo-Ni-Dual-Catalytic C(sp2)-C(sp3) Cross-Coupling Reactions with Mesoporous Graphitic Carbon Nitride as a Heterogeneous Organic Semiconductor Photocatalyst
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The synergistic combination of a heterogeneous organic semiconductor mesoporous graphitic carbon nitride (mpg-CN) and a homogeneous nickel catalyst with visible-light irradiation at room temperature affords the C(sp2)-C(sp3) cross-co
- Antonietti, Markus,Ghosh, Indrajit,K?nig, Burkhard,Khamrai, Jagadish,Savateev, Aleksandr
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p. 3526 - 3532
(2020/04/09)
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- One-pot Construction of Difluorinated Pyrrolizidine and Indolizidine Scaffolds via Copper-Catalyzed Radical Cascade Annulation
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A convenient approach to the synthesis of diverse difluorinated nitrogen-containing polycycles via a copper-catalyzed radical cascade annulation of amine-containing olefins and ethyl bromodifluoroacetate was developed. Three new bonds, including a Csp3 ?CF2 and two C?N bonds, are forged simultaneously in this strategy. Through this strategy, a series of difluorinated pyrrolizidine and indolizidine derivatives have been conveniently synthesized in good yields. (Figure presented.).
- Wang, Xiaoyang,Li, Miao,Yang, Yanyan,Guo, Minjie,Tang, Xiangyang,Wang, Guangwei
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supporting information
p. 2151 - 2156
(2018/04/26)
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- Cross-Coupling Reactions of Aryldiazonium Salts with Allylsilanes under Merged Gold/Visible-Light Photoredox Catalysis
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A method for the cross-coupling reactions of aryldiazonium salts with trialkylallylsilanes via merged gold/photoredox catalysis is described. The reaction is proposed to proceed through a photoredox-promoted generation of an electrophilic arylgold(III) intermediate that undergoes transmetalation with allyltrimethylsilane to form allylarenes.
- Akram, Manjur O.,Mali, Pramod S.,Patil, Nitin T.
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supporting information
p. 3075 - 3078
(2017/06/23)
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- Copper-Catalyzed Redox-Triggered Remote C-H Functionalization: Highly Selective Formation of C-CF3 and C-O Bonds
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A Cu-catalyzed remote sp3 C-H/unactivated alkenes functionalization reaction for the concomitant construction of C-CF3 and C-O bonds was described. An 1,5-H radical transfer involving an sp3 C-H bond adjacent to a nitrogen atom and an α-CF3-alkyl radical intermediate derived from unactivated alkenes was observed and demonstrated to proceed via the radical process. C-CF3 formation/1,5-H radical shift/remote functionalization of sp3 C-H bond.
- Li, Taotao,Yu, Peng,Lin, Jin-Shun,Zhi, Yonggang,Liu, Xin-Yuan
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supporting information
p. 490 - 494
(2016/06/01)
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- Phosphine-catalyzed remote β-C-H functionalization of amines triggered by trifluoromethylation of alkenes: One-pot synthesis of bistrifluoromethylated enamides and oxazoles
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An unprecedented phosphine-catalyzed remote β-C-H functionalization of amine derivatives triggered by trifluoromethylation of an alkene with Togni's reagent was disclosed. This reaction proceeded through the highly selective and concomitant activation of
- Yu, Peng,Zheng, Sheng-Cai,Yang, Ning-Yuan,Tan, Bin,Liu, Xin-Yuan
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supporting information
p. 4041 - 4045
(2015/03/30)
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- Allyl-transfer reaction from photoexcited hypervalent allylsilicon reagent toward dicyanobenzenes
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Photoreaction between dicyanobenzenes and a hypervalent allylsilicon reagent us ing 2,3-dihydroxynaphtha lene as a ligand on silicon efficiently proceeded to afford a llyl-substituted benzonitriles in moderate to good yields. The present photoreaction was
- Matsuoka, Daisuke,Nishigaichi, Yutaka
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supporting information
p. 163 - 165
(2015/02/19)
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- Enantioselective C-H bond functionalization triggered by radical trifluoromethylation of unactivated alkene
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An asymmetric unactivated alkene/C-H bond difunctionalization reaction for the concomitant construction of C-CF3 and C-Obonds was realized by using a Cu/Bronsted acid cooperative catalytic system, thus providing facile access to valuable chiral
- Yu, Peng,Lin, Jin-Shun,Li, Lei,Zheng, Sheng-Cai,Xiong, Ya-Ping,Zhao, Li-Jiao,Tan, Bin,Liu, Xin-Yuan
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supporting information
p. 11890 - 11894
(2015/02/05)
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- Palladium-catalyzed selective aminoamidation and aminocyanation of alkenes using isonitrile as amide and cyanide sources
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A mild and efficient palladium-catalyzed intermolecular aminoamidation and aminocyanation reaction of alkenes with a broad substrate scope has been developed. This cyclization process provides a valuable synthetic tool for obtaining substituted indolines, tetrahydroisoquinolines and pyrrolidines in good to excellent yields. This journal is
- Jiang, Huanfeng,Gao, Hanling,Liu, Bifu,Wu, Wanqing
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supporting information
p. 15348 - 15351
(2015/01/08)
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- Photosubstitution of dicyanoarenes by hypervalent allylsilicon reagents via photoinduced electron transfer
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Photosubstitution of dicyanoarenes with hypervalent allylsilicon reagents in the presence of anthracene efficiently proceeded to afford the allyl-substituted product in moderate to good yields. The efficiency for the present photoreaction was much higher
- Matsuoka, Daisuke,Nishigaichi, Yutaka
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p. 559 - 561
(2014/04/17)
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- Method for Allylating and Vinylating Aryl, Heteroaryl, Alkyl, and Alkene Halogenides Using Transition Metal Catalysis
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What is described is a process for preparing organic compounds of the general formula (I) R—R′??(I) by converting a corresponding compound of the general formula (II) R—X ??(II) in which X is fluorine, chlorine, bromine or iodine to an organomagnesium compound of the general formula (III) [M+]n[RmMgXkY1]??(III) wherein compounds of the formula (III) are reacted with a compound of the general formula (IV) characterized in that the reaction of (III) with (IV) is performed in the presence of a) catalytic amounts of an iron compound, based on the compound of the general formula (II), and optionally in the presence of b) a nitrogen-, oxygen- and/or phosphorus-containing additive in a catalytic or stoichiometric amount, based on the compound of the general formula (II).
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Paragraph 0062; 0063; 0064
(2013/07/25)
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- PhI(OAc)2-mediated iminobromination for synthesis of bromomethyl cyclic imines starting from alkenyl carbonitriles and Grignard reagents
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PhI(OAc)2-mediated iminobromination was developed starting from alkenyl carbonitriles and Grignard reagents. The present transformation is carried out by a sequence of nucleophilic addition of Grignard reagents to alkenyl carbonitriles to form
- Sanjaya, Stephen,Chiba, Shunsuke
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experimental part
p. 590 - 596
(2011/03/19)
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- Practical iron-catalyzed allylations of aryl grignard reagents
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An operationally simple iron-catalyzed reductive cross-coupling reaction between aryl halides and allyl electrophiles has been developed. The underlying domino process exhibits high versatility with respect to the allylic leaving group (acetate, tosylate, diethyl phosphate, methyl carbonate, trimethylsilanolate, methanethiolate, chloride, bromide) and high economic and environmental sustainability with respect to the catalyst system (0.2-5 mol% tris(acetylacetonato)iron(III), ligand-free) and reaction conditions (tetrahydrofuran, 0°C, 45 min).
- Mayer, Matthias,Czaplik, Waldemar M.,Von Wangelin, Axel Jacobi
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supporting information; scheme or table
p. 2147 - 2152
(2010/12/18)
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- Intramolecular hydroamination of unbiased and functionalized primary aminoalkenes catalyzed by a rhodium aminophosphine complex
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We report a rhodium catalyst that exhibits high reactivity for the hydroamination of primary aminoalkenes that are unbiased toward cyclization and that possess functional groups incompatible with more electrophilic hydroamination catalysts. The rhodium catalyst contains an unusual diaminophosphine ligand (L1) that binds to rhodium in a K3-P,O,P mode. The reactions catalyzed by this complex typically proceed at mild temperatures (room temperature to 70 °C) and occur with primary aminoalkenes lacking substituents on the alkyl chain that bias the system toward cyclization, with primary aminoalkenes containing chloride, ester, ether, enolizable ketone, nitrile, and unprotected alcohol functionality, and with primary aminoalkenes containing internal olefins. Mechanistic data imply that these reactions occur with a turnover-limiting step that is different from that of reactions catalyzed by late-transition-metal complexes of Pd, Pt, and Ir. This change in the turnover-limiting step and resulting high activity of the catalyst stem from favorable relative rates for protonolysis of the M-C bond to release the hydroamination product versus reversion of the aminoalkyl intermediate to regenerate the acyclic precursor. Probes of the origin of the reactivity of the rhodium complex of L1 imply that the aminophosphine groups lead to these favorable rates by effects beyond steric demands and simple electron donation to the metal center.
- Julian, Lisa D.,Hartwig, John F.
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supporting information; experimental part
p. 13813 - 13822
(2010/11/17)
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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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- Decarboxylative photosubstitution of dicyanobenzenes with aliphatic carboxylate ions
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The photoreaction of dicyanobenzenes with aliphatic carboxylate ions afforded alkylcyanobenzenes and alkyldicyanobenzenes via decarboxylative substitution. The redox-photosensitized reaction system was effective in improving the product yield. The efficie
- Itou, Tatsuya,Yoshimi, Yasuharu,Morita, Toshio,Tokunaga, Yuji,Hatanaka, Minoru
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experimental part
p. 263 - 269
(2009/04/07)
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- Deprotonative metalation of functionalized aromatics using mixed lithium-cadmium, lithium-indium, and lithium-zinc species
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In situ mixtures of CdCl2TMEDA (0.5 equiv; TMEDA = N,N,N',N'-tetramethylethylenediamine) or InCl3 (0.33 equiv) with [Li(tmp)] (tmp = 2,2,6,6-tetramethylpiperidino; 1.5 or 1.3 equiv, respectively) were compared with the previously described mixture of ZnCl2-TMEDA (0.5 equiv) and [Li(tmp)] (1.5 equiv) for their ability to deprotonate anisole, benzothiazole, and pyrimidine. [(tmp)3CdLi] proved to be the best base when used in tetrahydrofuran at room temperature, as demonstrated by subsequent trapping with iodine. The Cd-Li base then proved suitable for the metalation of a large range of aromatics including benzenes bearing reactive functional groups (CONEt2, CO2Me, CN, COPh) or heavy halogens (Br, I), and heterocycles (from the furan, thiophene, pyrrole, oxazole, thiazole, pyridine, and diazine series). Fivemembered heterocycles benefiting from doubly activated positions were similarly dideprotonated at room temperature. The aromatic lithium cadmates thus obtained were involved in palladium-catalyzed cross-coupling reactions or simply quenched with acid chlorides.
- Snegaroff, Katia,L'Helgoual'ch, Jean-Martial,Bentabed-Ababsa, Ghenia,Nguyen, Tan Tai,Chevallier, Floris,Yonehara, Mitsuhiro,Uchiyama, Masanobu,Derdour, Aicha,Mongin, Florence
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experimental part
p. 10280 - 10290
(2010/04/24)
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- Method of preparing organomagnesium compounds
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The present invention is directed to a reagent for use in the preparation of organomagnesium compounds as well as to a method of preparing such organomagnesium compounds. The present invention furthermore provides a method of preparing functionalized or unfunctionalized organic compounds as well as the use of the reagents of the present invention in the preparation of organometallic compounds and their reaction with electrophiles. Finally, the present invention is directed to the use of lithium salts - LiY in the preparation of organometallic compounds and their reactions with electrophiles and to an organometallic compound which is obtainable by the disclosed method.
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Page/Page column 13
(2010/02/14)
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- Method for producing Grignard compounds
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The invention relates to a process for preparing Grignard compounds of the formula I. The invention additionally relates to compounds of the formula I and to polymer-bound compounds of the formula Ia. The invention further relates to the use of the process for preparing substance libraries and to the use of the compounds of the formulae I and Ia in chemical synthesis.
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Page/Page column 11
(2008/06/13)
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- Process of heterocoupling by electrolytic microbattery, use of cobalt for implementing said coupling and composition for doing so
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This invention has as its object a process for preparation of vinyl aryl derivatives by an electrochemical path. This process is defined in that it consists in subjecting a composition that comprises a cobalt salt, an aromatic halide and a vinyl ester to the action of a metal that is at least as reducing as zinc. Application to organic synthesis.
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- Cobalt-catalyzed direct electrochemical cross-coupling between aryl or heteroaryl halides and allylic acetates or carbonates
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The electroreduction of a mixture of functionalized aromatic or heteroaromatic bromides or chlorides and allylic compounds such as acetates or carbonates in an electrochemical cell fitted with a sacrificial iron anode affords, in the presence of cobalt halide associated with pyridine as ligand in acetonitrile or DMF, the corresponding coupling product in good yields.
- Gomes, Paulo,Gosmini, Corinne,Perichon, Jacques
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p. 1142 - 1145
(2007/10/03)
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- Functionalized arylzinc compounds in ethereal solvent: Direct synthesis from aryl iodides and zinc powder and application to Pd-catalyzed reaction with allylic halides
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Arylzinc compounds, ArZnX, were conveniently prepared in high yields by the reaction of zinc powder with aryl iodides, which contain electron-withdrawing groups such as CO2CH3, CN, Br, or CF3 at the ortho-, meta- or para-position, or electron-donating groups such as CH3, OCH3, or H, at 70 °C in THF, at 100 °C, or at 130 °C in diglyme, respectively. Pd(dba)2 exhibited an outstanding efficient catalytic effect for the cross-coupling of these ethereal solutions of ArZnX with allylic halides to afford a variety of functionalized allylbenzenes in high yields; the reactions were mostly carried out at 0 °C for 5-30 min in the presence of 5 mol % of catalyst. The conversion of the aryl iodides to allylbenzenes via two reactions could be accomplished in one pot.
- Ikegami, Ryo,Koresawa, Akiko,Shibata, Takanori,Takagi, Kentaro
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p. 2195 - 2199
(2007/10/03)
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- New chemical cross-coupling between aryl halides and allylic acetates using a cobalt catalyst
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(Figure presented) The cobalt-catalyzed coupling reaction of aromatic halides and allylic acetates proceeds readily under mild conditions in the presence of the appropriate reducing agent to produce allylaromatic derivatives either in pure acetonitrile (aryl bromides) or in an acetonitrile/pyridine mixture (aryl chlorides).
- Gomes, Paulo,Gosmini, Corinne,Perichon, Jacques
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p. 1043 - 1045
(2007/10/03)
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- Selective halogen - Magnesium exchange reaction via organomagnesium ate complex
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Halogen-magnesium exchange of various aryl halides is achieved with a magnesium ate complex at low temperatures. Tributylmagnesate (nBu3MgLi) induces facile iodine-magnesium exchange at -78 °C. Dibutylisopropylmagnesate (iPrnBu2MgLi) is more reactive than nBu3MgLi, and this reagent accomplishes selective bromine-magnesium exchange at -78 °C. This procedure is utilized for the preparation of various polyfunctionalized arylmagnesium species. The exchange of alkenyl halides using this method proceeds with retention of configuration of the double bond.
- Inoue,Kitagawa,Shinokubo,Oshima
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p. 4333 - 4339
(2007/10/03)
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- Preparation of highly functionalized Grignard reagents by an iodine-magnesium exchange reaction and its application in solid-phase synthesis
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At -40°C aryl iodides that contain other functional groups can be selectively converted into Grignard reagents, which react with electrophiles such as benzaldehyde in the usual manner [Eq. (a)]. Aryl bromides and iodides that are immobilized as esters on a Wang resin behave analogously.
- Boymond, Laure,Rottlaender, Mario,Cahiez, Gerard,Knochel, Paul
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p. 1701 - 1703
(2007/10/03)
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- Photosubstitution of Dicyanobenzenes by Allylic Silanes, Germanes, and Stannanes via Photoinduced Electron Transfer
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Photoreactions of 1,2- and 1,4-dicyanobenzenes (o- and p-DCB) with allylic silanes, germanes, and stannanes in acetonitrile were studied under various conditions.In these photoreactions, one of cyano groups of o- and p-DCB was replaced by allylic groups.W
- Nakanishi, Kazuhisa,Mizuno, Kazuhiko,Otsuji, Yoshio
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p. 2371 - 2379
(2007/10/02)
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- PHOTOSUBSTITUTION OF DICYANOBENZENES BY GROUP 14 ORGANOMETALLIC COMPOUNDS VIA PHOTOINDUCED ELECTRON-TRANSFER. ADDITIVE AND MEDIUM EFFECTS ON PHOTOINDUCED ELECTRON TRANSFER REACTION
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The phenanthrene-sensitized photoreaction of 1,2- and 1,4-dicyanobenzenes with group 14 organometallic compounds containing allylic and benzylic groups in CH3CN afforded the corresponding 1- and 4-allylated benzonitriles in high yields.These photoreactions were accelerated by the addition of Mg(ClO4)2 and benzene derivatives.
- Mizuno, Kazuhiko,Nakanishi, Kazuhisa,Otsuji, Yoshio
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p. 1833 - 1836
(2007/10/02)
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- A NOVEL PHOTOSUBSTITUTION OF DICYANOBENZENES BY ALLYLIC AND BENZYLIC SILANES
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The photosubstitution of o- and p-dicyanobenzenes by allylic and benzylic silanes in acetonitrile occurred efficiently, giving the corresponding mono-allylated and benzylated cyanobenzenes.
- Mizuno, Kazuhiko,Ikeda, Munehiro,Otsuji, Yoshio
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p. 461 - 464
(2007/10/02)
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