14446-67-4Relevant academic research and scientific papers
Hydrosilylation of nitrogen-containing organic compounds: Model studies
Chechelska-Noworyta, Aleksandra,Owińska,Hasik, Magdalena
, (2019)
1,1,3,3-tetramethyldisiloxane (M2H) was used as the hydrosilylating agent for nitrogen-containing alkene derivatives: N-allylaniline (Naa), N-allylcyclohexylamine (Nach), N-allylpiperidine (Nap), 4-vinylpyridine (4VP) and 2-vinylpyri
Controlling the Coordination Sphere of Alkyllithiums Results in Selective Reactions with Allylic Amines
Kroesen, Ulrike,Unkelbach, Christian,Schildbach, Daniel,Strohmann, Carsten
, p. 14164 - 14168 (2017)
Described herein is a selective way to control the reaction of allylic amines with metalorganic bases depending on the amine handle as well as the metalorganic base is used. Depending on the number of coordinating groups within the amine handle either a selective carbometalation or deprotonation reaction can be performed. By changing the alkali metal within the base from lithium to either sodium or potassium, a change of chemoselectivity takes place and the reaction of piperidinoallylamine can be controlled.
Allylic Substitution using Heterogeneous Palladium Catalysts
Bergbreiter, David E.,Chen, Bushi
, p. 1238 - 1239 (1983)
Allylic substitution of the acetoxy group of allylic acetates by various nucleophiles is catalysed by heterogeneous palladium catalysts in the presence of triphenylphosphine.
Solvent interactions in the allylation of piperidine
Devender,Manikyamba
, p. 421 - 425 (2009)
The reaction between allylbromide and piperidine has been studied in different protic and aprotic solvents. The reaction is first order with respect to [allylbromide] and [piperidine]. A correlation analysis of the rate data with solvent properties shows that polarity (Y ), polarizability (P), and electrophilicity (E) of the solvent simultaneously influence the rate of reaction. From the regression analysis, information regarding the relative solvation of the reactants and the activated complex is obtained and a solvation model is proposed.
Diphosphines of dppf-type incorporating electron-withdrawing furyl moieties substantially improve the palladium-catalysed amination of allyl acetates
Fihri, Aziz,Hierso, Jean-Cyrille,Vion, Anthony,Duc, Hanh Nguyen,Urrutigoity, Martine,Kalck, Philippe,Amardeil, Regine,Meunier, Philippe
, p. 1198 - 1202 (2005)
Highly active Pd/diphosphine catalytic systems incorporating new, air-stable ferrocenyl-furylphosphines allow nucleophilic allylic amination at room temperature with unprecedented turnover frequencies. For instance, in the presence of 0.01 mol % catalyst the coupling of aniline to allyl acetate occurs at a TOF of more than 10,000 h-1; even the addition of the less nucleophile morpholine to allyl acetate is observed with a TOF of 4250 h -1. The amination of the sterically demanding geranyl acetate, a monoterpene derivative of interest in the flavour industry, at low catalyst loadings demonstrates the scope of this methodology, which provides in addition noticeable advantages in terms of economical (resource- and energy-saving) and sustainable chemistry (high selectivity, no additive, low metal content, and thus easier purification).
Photochemical Activation of Tertiary Amines for Applications in Studying Cell Physiology
Asad, Naeem,Deodato, Davide,Lan, Xin,Widegren, Magnus B.,Phillips, David Lee,Du, Lili,Dore, Timothy M.
supporting information, p. 12591 - 12600 (2017/09/23)
Representative tertiary amines were linked to the 8-cyano-7-hydroxyquinolinyl (CyHQ) photoremovable protecting group (PPG) to create photoactivatable forms suitable for use in studying cell physiology. The photoactivation of tamoxifen and 4-hydroxytamoxifen, which can be used to activate Cre recombinase and CRISPR-Cas9 gene editing, demonstrated that highly efficient release of bioactive molecules could be achieved through one- and two-photon excitation (1PE and 2PE). CyHQ-protected anilines underwent a photoaza-Claisen rearrangement instead of releasing amines. Time-resolved spectroscopic studies revealed that photorelease of the tertiary amines was extremely fast, occurring from a singlet excited state of CyHQ on the 70 ps time scale.
Silica-functionalized CuI: An efficient and selective catalyst for N-benzylation, allylation, and alkylation of primary and secondary amines in water
Shamim, Tahira,Kumar, Vineet,Paul, Satya
, p. 620 - 632 (2014/01/17)
Silica-functionalized CuI has been reported as an efficient and selective catalyst for the selective mono-N- and N,N-dibenzylation, allylation, and alkylation of primary amines with benzylic, allylic, and alkyl halides using NaOH as base in aqueous medium. By changing the reaction temperature, mono- or di-benzylation, allylation, or alkylation could be achieved in good yield and selectivity. Secondary amines have also been benzylated, allylated, and alkylated under similar conditions. SiO2-CuI has been characterized by Fourier transform-infrared, atomic absorption spectrometry, thermalgravimetric analysis, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy, and found to be highly selective and recyclable under the reaction conditions. [Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications for the following free supplemental resource(s): Full experimental and spectral details.] Copyright
Tsuji-trost N-allylation with allylic acetates by using a cellulose-palladium catalyst
Vaddula, Buchi Reddy,Saha, Amit,Varma, Rajender S.,Leazer, John
supporting information, p. 6707 - 6709 (2013/01/15)
Allylic amines were synthesized by a simple procedure using a biodegradable and easily recyclable heterogeneous cellulose-Pd catalyst through N-allylation of primary and secondary amines. The scope of this protocol includes aliphatic and benzylamines with substituted and unsubstituted allyl acetates and culminates in high yield syntheses. The highlights of the protocol include a ligand-free reaction, simple workup, and catalyst recyclability. Allylic amines were synthesized by N-allylation of primary and secondary amines through a simple and easy procedure involving the use of a heterogeneous cellulose-Pd catalyst; aliphatic and benzylamines underwent facile reaction with substituted and unsubstituted allyl acetates in high yields. Copyright
C-N bond cleavage of allylic amines via hydrogen bond activation with alcohol solvents in Pd-catalyzed allylic alkylation of carbonyl compounds
Zhao, Xiaohu,Liu, Delong,Guo, Hui,Liu, Yangang,Zhang, Wanbin
supporting information; experimental part, p. 19354 - 19357 (2012/01/06)
Hydrogen-bond-activated C-N bond cleavage of allylic amines was realized in Pd-catalyzed allylic alkylation to form the C-C bond product. The method could be expanded to a series of allylic amines and carbonyl compounds with excellent results. It provides a new and convenient access to C-C bond formation based on Pd-catalyzed allylic alkylation of allylic amines by using only inexpensive alcohol solvents.
The Pauson-Khand reaction: A gas-phase and solution-phase examination using electrospray ionization mass spectrometry
Henderson, Matthew A.,Luo, Jingwei,Oliver, Allen,McIndoe, J. Scott
experimental part, p. 5471 - 5479 (2011/12/13)
A series of dicobalt hexacarbonyl complexes with charged alkyne ligands were prepared to enable the study of the Pauson-Khand reaction using ESI-MS. The hexacarbonyl complexes can be activated in the gas phase through removal of a CO ligand. The resulting pentacarbonyl ions react readily with alkenes, and no discrimination between alkenes was found for this step, indicating that alkene association is not rate determining in the intermolecular reaction. Solution-phase ESI-MS studies on a system set up for intramolecular reactivity revealed only the hexacarbonyl complex as a detectable intermediate, and the reaction was shown to have a large enthalpy and entropy of activation, consistent with ligand dissociation being rate limiting in the reaction.
