76842-47-2Relevant academic research and scientific papers
A potassium magnesiate complex: Synthesis, structure and catalytic intermolecular hydroamination of styrenes
Guan, Bing-Tao,Liu, Yu-Feng,Zhai, Dan-Dan,Zhang, Xiang-Yu
supporting information, (2022/01/19)
A new heterobimetallic potassium magnesiate complex KMg[N(SiMe3)2]2Bn (Bn = PhCH2-) was synthesized by simply mixing magnesium amide and potassium benzyl in toluene. The TMEDA-ligated potassium magnesiate comple
Cine-Silylative Ring-Opening of α-Methyl Azacycles Enabled by the Silylium-Induced C-N Bond Cleavage
Zhang, Jianbo,Chang, Sukbok
, p. 12585 - 12590 (2020/08/21)
Described herein is the development of a borane-catalyzed cine-silylative ring-opening of α-methyl azacycles. This transformation involves four-step cascade processes: (i) exo-dehydrogenation of alicyclic amine, (ii) hydrosilylation of the resultant enamine, (iii) silylium-induced cis-β-amino elimination to open the ring skeleton, and (iv) hydrosilylation of the terminal olefin. The present borane catalysis also works efficiently for the C-N bond cleavage of acyclic tertiary amines. On the basis of experimental and computational studies, the silicon atom was elucidated to play a pivotal role in the β-amino elimination step.
Ruthenium-catalyzed N-alkylation of amines with alcohols under mild conditions using the borrowing hydrogen methodology
Enyong, Arrey B.,Moasser, Bahram
, p. 7553 - 7563 (2014/09/17)
Using a simple amino amide ligand, ruthenium-catalyzed one-pot alkylation of primary and secondary amines with simple alcohols was carried out under a wide range of conditions. Using the alcohol as solvent, alkylation was achieved under mild conditions, even as low as room temperature. Reactions occurred with high conversion and selectivity in many cases. Reactions can also be carried out at high temperatures in organic solvent with high selectivity using stoichiometric amounts of the alcohol.
Selective N-alkylation of primary amines with R-NH2·HBr and alkyl bromides using a competitive deprotonation/protonation strategy
Bhattacharyya, Shubhankar,Pathak, Uma,Mathur, Sweta,Vishnoi, Subodh,Jain, Rajeev
, p. 18229 - 18233 (2014/05/20)
Monoalkylation of primary amines using amine hydrobromides and alkyl bromides has been carried out. Under controlled reaction conditions the reactant primary amine was selectively deprotonated and made available for reaction, while the newly generated secondary amine remained protonated, and did not participate in alkylation further. Reaction was carried out under mild reaction conditions and was applicable to a wide range of primary amines and alkyl bromides.
Ruthenium-catalyzed formation of tertiary amines from nitriles and alcohols
Liu, Saiwen,Chen, Ru,Deng, Guo-Jun
supporting information; experimental part, p. 489 - 491 (2011/06/25)
A ruthenium-catalyzed tertiary-amine formation was developed using the borrowing hydrogen strategy. Various tertiary amines were obtained efficiently from nitriles and primary alcohols. Two possible pathways were found for the tertiaryamine formation under RuCl3/dppf catalytic conditions. The nitriles mainly act as a nitrogen source in this kind of transformation.
Base-catalyzed anti-Markovnikov hydroamination of vinylarenes - Scope, limitations and computational studies
Horrillo-Martinez, Patricia,Hultzsch, Kai C.,Gil, Adria,Branchadell, Vicenc
, p. 3311 - 3325 (2008/02/10)
The hydroamination of vinylarenes with primary and secondary amines was studied with catalytic amounts as low as 2 mol-% of LiN(SiMe3) 2/TMEDA. Reactions proceeded readily at 120°C in the absence of solvent to give selective anti-Markovnikov addition. Slow addition was observed at 25°C with either electron-deficient p-chlorostyrene or secondary cyclic amines such as pyrrolidine, piperidine, or morpholine. Primary amines were prone to a second hydroamination reaction to form tertiary amine byproducts. The selectivity for the mono(hydroamination) products could be improved with a two-fold excess of the amine. KN(SiMe3)2 showed higher catalytic activity but lower selectivity in comparison to that of LiN(SiMe 3)2, resulting in undesired C-H-activation by-products. The mechanism of the lithium-catalyzed hydroamination and the influence of TMEDA was studied with density functional theory. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
Scope and mechanistic insights into the use of tetradecyl(trihexyl) phosphonium bistriflimide: A remarkably selective ionic liquid solvent for substitution reactions
McNulty, James,Nair, Jerald J.,Cheekoori, Sreedhar,Larichev, Vladimir,Capretta, Alfredo,Robertson
, p. 9314 - 9322 (2007/10/03)
A survey of substitution reactions conducted in a phosphonium bistriflimide ionic liquid is presented. The results demonstrate high selectivity favoring substitution over typically competitive elimination and solvolytic processes even when challenging secondary and tertiary electrophiles are employed. The first reports of Kornblum substitution reactions in an ionic liquid are described that proceed with very high chemoselectivity in favor of nitro over nitroso products and elimi nation side products. The structure-reactivity study indicates that these reactions proceed through a narrow spectrum of pathways ranging from straight SN2 to a preassociation pathway along a saddle point that approaches the SN1 limit. The barrier to the formation of dissociated carbocations is attributed to the structural features of this ionic liquid that favor intervention of the associated nucleophile over dissociation, also preventing cross over to E1 processes. The lack of any basic entity in the phosphonium bistriflimide ionic liquid appears to prevent any potential base-mediated elimination reactions, which makes this a highly selective medium for use in general substitution reactions.
Lithium Alkylamide-Catalyzed Addition Reaction of Alkylamines to Vinyl Monomers. III. Addition Reaction of p-Substituted Benzylamines to Styrene and Divinylbenzenes
Hamana, Hiroshi,Iwasaki, Fuminori,Nagashima, Hiroyoshi,Hattori, Kazuhisa,Hagiwara, Tokio,Narita, Tadashi
, p. 1109 - 1113 (2007/10/02)
The lithium alkylamide-catalyzed addition reaction of p-substituted benzyamines with m- and p-divinylbenzene was examined in order to synthesize new styrene derivatives.Though divinylbenzene possesses two vinyl groups, 1:1 adducts, the N-(p-substituted benzyl)vinylphenethylamines (6, 8) were found to be prepared selectively.The reaction with styrene was also examined as a model reaction.From kinetic studies, the Hammett ρ values for the addition reaction of p-substituted benzylamines to the styrene, m-divinylbenzene and p-divinylbenzene, were -0.72, -0.67, and -1.1, respectively, at 50 deg C.
