- Photoinduced Cross-Coupling of Aryl Iodides with Alkenes
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A protocol for photoinduced cross-coupling of aryl iodides having polar π-functional groups or elongated π-conjugation with alkenes has been developed. The radical cascade mechanism involving generation of aryl radicals via C-I bond homolysis of photoexcited aryl iodides and their subsequent addition to alkenes is proposed. The method enables iodide-selective cross-coupling over other halogen leaving groups with functional group compatibility on both arene and alkene motifs.
- Liu, Yuliang,Li, Haoyu,Chiba, Shunsuke
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supporting information
p. 427 - 432
(2021/01/26)
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- A General Photocatalytic Route to Prenylation
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Prenylation is an essential reaction on which nature relies to modify properties of molecules and build terpenoids, but remains a challenging chemical reaction. Aiming to capitalize on recent advances in photocatalysis to easily and cleanly generate a broad range of carbon based radicals, we have developed a prenyl transfer reagent that is captured by transiently generated radicals. The reagent can be made in bulk, is bench stable, and broadly applicable such that it can be used with existing photocatalytic methods with very few changes to reaction conditions. Ultimately, this provides a true drop-in solution for prenylation, expanding the scope of substrates that can be readily prenylated.
- Rathnayake, Manjula D.,Weaver, Jimmie D.
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supporting information
p. 1433 - 1438
(2019/06/13)
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- Palladium-catalyzed allyl cross-coupling reactions with in situ generated organoindium reagents
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Inter- and intramolecular palladium-catalyzed allyl cross-coupling reactions, using allylindium generated in situ from allyl halides and indium, is demonstrated. Allylindium compounds may be effective nucleophilic coupling partners in palladium-catalyzed cross-coupling reactions. A variety of allyl halides, such as allyl iodide, allyl bromide, crotyl bromide, prenyl bromide, geranyl bromide, and 3-bromocyclohexene afforded the allylic cross-coupling products in good to excellent yields. Stereochemistry of the double bond is retained in the allylic cross-coupling reactions. Electrophilic cross-coupling partners, such as aryl and vinyl halides, dibromoolefin, alkynyl iodide, and aryl and vinyl triflates participate in these reactions. The presence of various substituents, such as n-butyl, ketal, acetyl, ethoxycarbonyl, nitrile, N-phenylamido, nitro, and chloride groups on the aromatic ring of electrophilic coupling partners showed little effect on the efficiency of the reactions. The present conditions work equally well for not only intermolecular but also intramolecular palladium-catalyzed cross-coupling reactions. These methods provide an efficient synthetic method for the introduction of an allyl group, which can be easily further functionalized to afford an sp2- and sp-hybridized carbon. The present method complements existing synthetic methods as a result of advantageous features such as easy preparation and handling, thermal stability, high reactivity and selectivity, operational simplicity, and low toxicity of allylindium reagents.
- Lee, Kooyeon,Kim, Hyunseok,Mo, Juntae,Lee, Phil Ho
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scheme or table
p. 2147 - 2157
(2011/10/31)
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- α-Selective cross-coupling reaction of allyltrifluorosilanes: Remarkable ligand effect on the regiochemistry
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The cross-coupling reaction of allyltrifluorosilanes with aryl halides or aryl triflates promoted by a fluoride salt takes place at the α-carbon of the allyltrifluorosilanes in the presence of a catalytic amount of PdCl2[Ph2P(CH
- Hatanaka, Yasuo,Goda, Ken-Ichi,Hiyama, Tamejiro
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p. 6511 - 6514
(2007/10/02)
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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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- Reactivity of Aryl Vinyl Di-?-methane Systems. Mechanistic and Exploratory Organic Photochemistry
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The di-?-methane rearrangement of a series of meta and para substituted arylvinylmethane reactants was investigated with the aim of determiningthe patterns of reactivity in systems in which initial excitation is localized in the aryl moiety.Thus the photo
- Zimmerman, Howard E.,Swafford, Richard L.
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p. 3069 - 3083
(2007/10/02)
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