- Synthesis of Polycyclic Aromatic Hydrocarbons Decorated by Fluorinated Carbon Acids/Carbanions
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The carboarylation reaction of biphenyl-alkynes was successfully triggered by electrophilic attack of 1,1-bis(triflyl)ethylene on the alkyne moiety to give polycyclic aromatic hydrocarbons (PAHs) decorated by superacidic carbon acid functionality. Neutralisation of thus obtained acids with NaHCO3 yielded the corresponding sodium salts, which showed improved solubility in both aqueous and organic solvents.
- Hoshikawa, Shoki,Yanai, Hikaru,Martín-Mejías, Irene,Lázaro-Milla, Carlos,Aragoncillo, Cristina,Almendros, Pedro,Matsumoto, Takashi
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p. 16112 - 16116
(2021/10/12)
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- Regioselective Diboron-Mediated Semireduction of Terminal Allenes
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A method for the regioselective reduction of the terminal double bond of 1,1-disubstituted allenes has been developed. In the presence of a palladium catalyst, tetrahydroxydiboron and stoichiometric water, allene semireduction proceeds in high yield to afford Z-alkenes selectively.
- Gates, Ashley M.,Santos, Webster L.
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supporting information
p. 4619 - 4624
(2019/12/11)
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- A convenient access to allylic triflones with allenes and triflyl chloride in the presence of (EtO)2P(O)H
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A simple method for the preparation of allylic triflones from allenes and triflyl chloride in the presence of (EtO)2P(O)H has been developed. The features of this reaction are catalyst-free and simple starting substrates. This method tolerates diverse functional groups and substituted allylic triflones are obtained in moderate to good yields.
- Ni, Jixiang,Jiang, Yong,An, Zhenyu,Lan, Jingfeng,Yan, Rulong
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supporting information
p. 7343 - 7345
(2019/06/27)
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- Synthesis of terminal allenes through copper-mediated cross-coupling of ethyne with N-tosylhydrazones or α-diazoesters
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Ethyne is employed as coupling partner in coppermediated cross-coupling reactions with N-tosylhydrazones and α-diazoacetate, leading to the development of a new synthetic method for terminal allenes. With this novel coupling method, the terminal allenes w
- Ye, Fei,Wang, Chengpeng,Ma, Xiaoshen,Hossain, Mohammad Lokman,Xia, Ying,Zhang, Yan,Wang, Jianbo
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p. 647 - 652
(2016/09/12)
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- Photoinduced skeletal rearrangement of 1,1-diarylspiropentanes
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The photochemical reactivities of 1,1-diarylspiropentanes 1a-c have been investigated under various photolysis conditions. Upon direct photolysis or acetone-sensitized photolysis, 1 underwent skeletal rearrangement to afford methylidenecyclobutanes 2, 3 and 4. A mechanism involving diradical intermediates has been proposed. Also studied were the photochemical and thermal reactions of the electron donor-acceptor (EDA) complexes of 1 with tetracyanoethylene (TCNE). Photoirradiation of the charge-transfer (CT) absorption bands of the EDA complexes resulted in the skeletal rearrangement of 1 to 2 and 3, with concomitant formation of TCNE adducts 11b,c and 12a-c. The X-ray structure of 11c is reported. A mechanism involving ion radical pairs [1?+, TCNE?-] is proposed for the photoreaction. In contrast, no skeletal rearrangement was observed in the thermal reaction of the EDA complexes although i1b and 11c were produced.
- Takahashi, Yasutake,Ohaku, Hitoshi,Morishima, Shin-Ichi,Suzuki, Takanori,Ikeda, Hiroshi,Miyashi, Tsutomu
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p. 319 - 325
(2007/10/03)
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- Photocyclization between Quinones and Allenes via Photoinduced Electron Transfer
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Photochemical reactions of halo-1,4-naphthoquinones with 1,1-diphenylallenes afforded spiropyran adducts derived from cycloaddition between carbonyl group of quinone and allene in good yield.In the photoreactions of 2,3-dichloro-1,4-naphthoquinone with monophenylallenes, cycloadducts were obtained in addition to spiropyran derivatives.Considering the relationship between formation of spiropyran adducts and the free energy changes (ΔG) together with substituent effects, solvent effects, and CIDNP (chemically induced dynamic nuclear polarization), we propose an electron-transfer mechanism.That is, radical ion pair formation from excited triplet quinone and allene is followed by conversion to a biradical.Subsequent bond formation between the ketyl radical in quinone moiety and ortho position of the phenyl substituents on the allene skeleton leads to the spiropyran adduct after subsequent 1,5-hydrogen shift.
- Maruyama, Kazuhiro,Imahori, Hiroshi
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p. 2692 - 2702
(2007/10/02)
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- A NOVEL ORTHO-SUBSTITUENT EFFECT ON FORMATION OF VINYL CATIONS IN THE PHOTOLYSIS OF VINYL BROMIDES
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Introduction of a substituent into ortho-position of β-aryl group in a vinyl bromide resulted in the preferential formation of a vinyl cation in the photolysis.It is considered that the steric repulsion of β-aryl groups makes a convenient conformation for an electron transfer from the aromatic ring to the halogen atom in the radical pair.
- Kitamura, Tsugio,Muta, Tomonobu,Kobayashi, Shinjiro,Taniguchi, Hiroshi
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p. 643 - 644
(2007/10/02)
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