- COMPETITION BETWEEN n,?- AND n,?-ORBITAL INTERACTIONS IN CHLORINATED ETHERS R-O-CHClR1
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Using the AM-1 method, we have studied CH2=CH-O-CHClR1 molecules (R1 = H, Me).We have shown that the sc conformation with respect to the Csp3-O bond is preferred.We have systematized the 35Cl NOR data on the degree of manifestation of the generalized anomeric effect in R-OCHClR1 2C(=O)> molecules.We have established that enhancement of n,? conjugation in the R-O fragment leads to weakening of the n,? interaction in the O-C-Cl triad.
- Bredikhin, A. A.,Kirillovich, V. A.,Safin, I. A.,Vereshchagin, A. N.
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Read Online
- Nickel-Catalyzed Asymmetric Reductive Cross-Coupling between Heteroaryl Iodides and α-Chloronitriles
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A Ni-catalyzed asymmetric reductive cross-coupling of heteroaryl iodides and α-chloronitriles has been developed. This method furnishes enantioenriched α,α-disubstituted nitriles from simple organohalide building blocks. The reaction tolerates a variety of heterocyclic coupling partners, including pyridines, pyrimidines, quinolines, thiophenes, and piperidines. The reaction proceeds under mild conditions at room temperature and precludes the need to pregenerate organometallic nucleophiles.
- Kadunce, Nathaniel T.,Reisman, Sarah E.
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supporting information
p. 10480 - 10483
(2015/09/28)
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- Mechanism of halogen exchange in ATRP
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Detailed mechanistic studies reveal that halogen exchange (HE) in ATRP can occur not only by a radical pathway (atom transfer) but also by an ionic pathway (SN2 reaction) because Cu(I)(L)X and Cu (II)(L)X2 complexes contain weakly associated halide anion that can participate in the SN2 reaction with alkyl halide (ATRP initiator). Both pathways were kinetically studied, and their contributions to the HE process were quantitatively evaluated for seven alkyl halides and three Cu(I)(L)Cl complexes. Radical pathway dominates the HE process for 3° and 2° alkyl bromides with more active complexes such as Cu (I)(TPMA)Cl. Interestingly, ionic pathway dominates for 1° alkyl bromides and less active ATRP catalysts. These studies also revealed that degree of association of alkyl halide anion depends on the structure of copper complexes. In addition, radical pathway is accompanied by the reverse reactions such as deactivation of radicals to alkyl bromides and also activation of alkyl chlorides, reducing the efficiency of halogen exchange.
- Peng, Chi-How,Kong, Jing,Seeliger, Florian,Matyjaszewski, Krzysztof
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scheme or table
p. 7546 - 7557
(2012/07/28)
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- Reinvestigation of the reaction of trichloroacetyl chloride and acrylonitrile in the preparation of 3,5,6-trichloropyridin-2-ol
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The synthesis of 3,5,6-trichloropyridin-2-ol via the CuCl-catalyzed reaction of trichloroacetyl chloride and acrylonitrile under both pressure and atmospheric conditions and the hydrolysis of the reaction mixture were reinvestigated. The products and byproducts formed in each case, before the hydrolysis step, were characterized, and the factors causing their formation are discussed. It was found that two newly identified byproducts influence the yield of the reaction.
- Fakhraian,Moghimi,Bazaz,Hadj-Ghanbary,Sadeghi
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p. 329 - 333
(2013/09/06)
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- PREPARATION OF NITRILES BY DEHYDRATION OF PRIMARY CARBOXAMIDES WITH A SUPPORTED PHOSPHORUS PENTOXIDE REAGENT
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The use of a supported phosphorus pentoxide reagent in the synthesis of selected nitriles is discussed.
- Kaiser, Delene A.,Kaye, Perry T.,Pillay, Lavinthren,Roos, Gregory H. P.
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p. 883 - 888
(2007/10/02)
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