54321-41-4Relevant academic research and scientific papers
Quantitative α-alkylation of primary nitriles
Rojas, Giovanni,Baughman, Travis W.,Wagener, Kenneth B.
, p. 3923 - 3931 (2008/03/14)
A synthetic pathway that produces alkyl α,ω-cyanodiolefins in quantitative yield is described, applying chemistry that is based on simple α-alkylation of alkyl nitriles. Three amide bases, lithium 2,2,6,6-tetramethylpiperidide, lithium diisopropylamide, and sodium amide, are used to create the α-carbanions that undergo substitution with various alkylating agents. Optimization leads to essentially quantitative conversions for every substrate/example reported herein, which will prove useful in many synthetic schemes. Copyright Taylor & Francis Group, LLC.
Nucleophilic displacement reactions in ionic liquids: Substrate and solvent effect in the reaction of NaN3 and KCN with alkyl halides and tosylates
Chiappe, Cinzia,Pieraccini, Daniela,Saullo, Paola
, p. 6710 - 6715 (2007/10/03)
Room-temperature ionic liquids have been used as environmentally benign solvents for the preparation of primary and secondary alkyl azides and nitriles under solid-RTIL phase-transfer conditions. The reaction of primary, secondary, and tertiary halides or tosylates with KCN and NaN3 has been investigated in three ionic liquids ([bmim][PF6], [bmim][N(Tf) 2], and [hpyr] [N(Tf)2]). The observed nucleofugacity scales for the reaction of NaN3 are similar to those reported for the same process in cyclohexane, indicating that in these solvents it is possible to evidence the intrinsic ability to depart of leaving groups. Changes in the nature of the IL cation or anion determine significant modifications in reactivity of the investigated substrates. Reactivity has been interpreted considering a gradual shift of the mechanism from concerted SN2 (primary substrates) to stepwise SN1 (tertiary substrate, 3), through the nucleophilically assisted formation of an ion pair intermediate, in the case of 2d.
Reductive alkylation of electronegatively-substituted alkenes by alkylmercury halides
Russell, Glen A.,Shi, Bing Zhi,Jiang, Wan,Hu, Shuiesheng,Kim, Byeong H.,Baik, Woonphil
, p. 3952 - 3962 (2007/10/02)
Photolysis of alkylmercury halides in the presence of electronegatively-substituted 1-alkenes yields adduct radicals [RCH2CH(EWG).] that in some cases react with RHgX to form RCH2CH(HgX)(EWG), e.g., EWG = (EtO)2PO or PhSO2. When the EWG is carbonyl or cyano, the resonance stabilized adduct radicals fail to react with the alkyl mercury halide. In these cases photolysis with RHgCl/KI in Me2SO leads to the adduct mercurial via reaction of the adduct radicals with RHgI2-. The reactions of tertiary-enolyl adduct radicals are inefficient with RHgX/KI, and disproportionation of the adduct radicals is the major reaction pathway. For secondary- or tertiary-adduct radicals the reductive alkylation products are formed in excellent yield by reaction with RHgCl and silyl hydrides in Me2SO solution in a process postulated to involve RHgH as an intermediate. The relative reactivities of a number of α,β-unsaturated systems toward t-Bu. have been measured by competitive techniques. The results demonstrate a high reactivity of s-cis enones relative to the s-trans conformers.
Hydrocyanation of α,ω-Diynes Catalyzed by Tetracyanonickelate. Regiospecific Synthesis of a New Series of Acyclic Dinitriles
Funabiki, Takuzo,Sato, Yoshihiro,Yoshida, Satohiro
, p. 2863 - 2864 (2007/10/02)
Hydrocyanation of α,ω-diynes without the use of HCN has been described.Cyanonickelate, prepared by reducing 2- with NaBH4 or Zn in the presence of excess KCN in water or ethylene glycol, catalyzes hydrocyanation of α,ω-diynes, HCC(CH2)nCCH to give quantitatively CH3CH(CN)(CH2)nCH(CN)CH3, a new series of acyclic dinitriles.Importance of the preliminary formation of a (?-acetylene)nickel(0) complex for the hydrocyanation has been suggested.
