- Carbolithiation of simple terminal and strained internal alkenes by the naphthalene and the biphenyl dianion: New modes of reactivity of highly reduced organic species in solution
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Dianions derived from arenes of high reduction potential (biphenyl, naphthalene) and Li(s) can carbometallate propene, isobutene or norbornene among other alkenes, in an intermolecular fashion. This reaction runs at room temperature to afford p
- Melero, Cristobal,Guijarro, Albert,Baumann, Vitus,Perez-Jimenez, Angel J.,Yus, Miguel
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p. 5514 - 5526
(2008/09/17)
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- Reactivity in the upper limits of the reduction potential in solution: arene dianion intermolecular carbolithiation of alkenes
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Lithium salts of dianions derived from arenes of high reduction potential (biphenyl, naphthalene) can carbometallate terminal alkenes (propene, isobutene) in an intermolecular fashion, affording partially dearomatized alkylated aryl anions, which are susc
- Melero, Cristóbal,Guijarro, Albert,Yus, Miguel
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p. 6267 - 6271
(2007/10/03)
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- Substitution Reactions of Secondary Halides and Epoxides with Higher Order, Mixed Organocuprates, R2Cu(CN)Li2: Synthetic, Stereochemical, and Mechanistic Aspects
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Higher order cuprates, represented by the general formula R2Cu(CN)Li2, are readily prepared from copper cyanide and 2 equiv of an organolithium.These novel reagents react readily and efficiently with secondary unactivated iodides and bromides affording products of substitution.Likewise, mono-, di-, and trisubstituted epoxides undergo ring opening leading to the corresponding alcohols in excellent yields.The effects of solvent, temperature, gegenion, and variations in ligands are discussed.Replacement of the second equivalent of RLi by CH3Li strongly encouragestransfer of R over CH3 in R(CH3)Cu(CN)Li2 with halides.Use of PhLi as RRLi in place of one RTLi (i.e.RT(Ph)Cu(CN)Li2) is suggested for oxirane cleavage.The stereochemical implications associated with both couplings are also addressed.
- Lipshutz, Bruce H.,Wilhelm, Robert S.,Kozlowski, Joseph A.,Parker, David
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p. 3928 - 3938
(2007/10/02)
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