10316-00-4Relevant articles and documents
The different, but interesting behaviors of benzyl systems in the Willgerodt-Kindler reaction under solvent-free conditions
Aghapoor, Kioumars,Darabi, Hossein Reza,Tabar-Heydar, Kourosh
, p. 1183 - 1187 (2002)
On the benzyl system, bearing various functional groups, have been carried out the Willgerodt-Kindler reaction to obtain thiobenzmorpholide (1). The reactions, under solvent-free conditions, were performed in both classical (reflux, room temperature) and
Heterogeneous Ni catalysts for N-alkylation of amines with alcohols
Shimizu, Ken-Ichi,Imaiida, Naomichi,Kon, Kenichi,Hakim Siddiki,Satsuma, Atsushi
, p. 998 - 1005 (2013)
Nickel nanoparticles loaded onto various supports (Ni/MOx) have been prepared and studied for the N-alkylation of amines with alcohols. Among the catalysts, Ni/θ-Al2O3 prepared by in situ H 2-reduction of NiO/θ-Al2O3 shows the highest activity, and it acts as reusable heterogeneous catalyst for the alkylation of anilines and aliphatic amines with various alcohols (benzyl and aliphatic alcohols) under additive free conditions. Primary amines are converted into secondary amines and secondary amines into tertiary amines. For the reaction of aniline with an aliphatic alcohol the catalyst shows higher turnover number (TON) than precious metal-based state-of-the-art catalysts. Mechanistic studies suggest that the reaction proceeds through a hydrogen-borrowing mechanism. The activity of Ni catalysts depends on the nature of support materials; acid-base bifunctional supports give higher activity than basic or acidic supports, indicating that acid-base sites on supports are necessary. The presence of basic (pyridine) or acidic (acetic acid) additive in the solution decreased the activity of Ni/θ-Al2O3, which suggests the cooperation of the acid-base site of θ-Al2O3. For a series of Ni/θ-Al2O3 catalysts with different particle size, the turnover frequency (TOF) per surface Ni increases with decreasing Ni mean particle size, indicating that low-coordinated Ni species and/or metal-support interface are active sites. From these results, we propose that the active site for this reaction is metal-support interface, where low-coordinated Ni0 atoms are adjacent to the acid-base sites of alumina.
On the non-classical course of Polonowski reactions of N-benzylmorpholine- N-oxide (NBnMO)
Rosenau, Thomas,Schmid, Peter,Kosma, Paul
, p. 3483 - 3487 (2005)
The Polonowski reaction of NBnMO (4) afforded tropone (10) and the novel isoindole 11 besides the expected products benzaldehyde and acetmorpholide, in a temperature-dependent ratio. The reaction proceeded via two primary carbenium-iminium ion intermediates, an exo-centered species 5 which underwent a benzylium-tropylium type rearrangement, and a ring-centered species 6, which reacted further to isoindole 11 by intramolecular electrophilic substitution. The experimental findings were in good agreement with DFT computational data.
Bis(alkyl) scandium and yttrium complexes coordinated by an amidopyridinate ligand: Synthesis, characterization and catalytic performance in isoprene polymerization, hydroelementation and carbon dioxide hydrosilylation
Gurina,Kissel,Lyubov,Luconi,Rossin,Tuci,Cherkasov,Lyssenko,Shavyrin,Ob'Edkov,Giambastiani,Trifonov
, p. 638 - 650 (2020)
New neutral bis(alkyl) Sc and Y complexes [N,Npy,N-]Ln(CH2SiMe3)2(THF)n [n = 0, Ln = Sc (1Sc), Y (1Y); n = 1, Ln = Y (1YTHF)] stabilized by a tridentate monoanionic amidopyridinate ligand were straightforwardly prepared by alkane elimination, upon mixing ligand [N,Npy,N-]H and metal precursor Ln(CH2SiMe3)3(THF)2 in toluene at 0 °C. Depending on the work-up conditions, yttrium bis(alkyl)s were isolated as either a pentacoordinate Lewis base free complex [N,Npy,N-]Y(CH2SiMe3)2 (1Y) or as a hexacoordinate THF adduct [N,Npy,N-]Y(CH2SiMe3)2THF (1YTHF). For the smaller Sc ion the only solvent-free complex [N,Npy,N-]Y(CH2SiMe3)2 (1Sc) was isolated as a pentacoordinate species irrespective of the reaction/work-up/crystallization conditions applied. Complexes 1Ln (Ln = Y, Sc) and 1YTHF were scrutinized as pre-catalysts in ternary catalytic systems Ln/borate/AliBu3 (borate = [HNMe2Ph][B(C6F5)4] or [Ph3C][B(C6F5)4]), applied to isoprene (IP) polymerization, providing moderate activity albeit high selectivity with predominant formation of 1,4-cis polyisoprene (up to 99%). The same complexes proved to be effcient catalysts also for the intermolecular hydrolelementation of styrene with various EH sustrates (pyrrolidine, morpholine, Ph2PH, PhPH2, PhSH) affording linear anti-Markovnikov addition products exclusively. After a preliminary activation by B(C6F5)3, selected bis(alkyl) complexes from this series have been finally used as valuable pre-catalysts for the CO2 hydrosylilation to CH4 in the presence of organosilanes as reducing agents (PhMe2SiH, PhSiH3, Et2MeSiH).
Cesium carbonate-catalyzed reduction of amides with hydrosilanes
Xie, Weilong,Zhao, Mengdi,Cui, Chunming
, p. 7440 - 7444 (2013)
Cesium carbonate has been found to be an effective catalyst for the reduction of tertiary carboxamides with the simple, commercially available PhSiH3 under solvent-free conditions. The catalytic system can effectively reduce a range of amides under relatively mild conditions (from room temperature to 80 C) to yield the corresponding amines in good to excellent yields (71-100%) and thus has the potential for practical applications.
Fast continuous alcohol amination employing a hydrogen borrowing protocol
Labes, Ricardo,Mateos, Carlos,Battilocchio, Claudio,Chen, Yiding,Dingwall, Paul,Cumming, Graham R.,Rincón, Juan A.,Nieves-Remacha, Maria José,Ley, Steven V.
, p. 59 - 63 (2019)
A continuous flow method for the direct conversion of alcohols to amines via a hydrogen borrowing approach is reported. The method utilises a low loading (0.5%) of a commercial catalyst system ([Ru(p-cymene)Cl2]2 and DPEPhos), reagent grade solvent and is selective for primary alcohols. Successful methylation of amines using methanol and the direct dimethylamination of alcohols using commercial dimethylamine solution are reported. The synthesis of two pharmaceutical agents Piribedil (5) and Buspirone (25) were accomplished in good yields employing these new methods.
Reductive amination of carbonyl compounds over silica supported palladium exchanged molybdophosphoric acid catalysts
Srivani,Prasad, P. S. Sai,Lingaiah
, p. 389 - 396 (2012)
Palladium exchanged molybdophosphoric acid supported on silica is reported as a highly effective catalyst for direct reductive amination of carbonyl compounds. The catalysts are characterized by X-ray diffraction and FT-infrared spectroscopy. The characterization results support the existence of Keggin ion of heteropoly molybdate on silica. The catalyst is facile, water tolerable and environmentally benign for reductive amination. A variety of secondary and tertiary amines can be synthesized over this catalyst in excellent yields under mild reaction conditions. A plausible reaction mechanism is proposed for the reductive amination of carbonyl compounds over this catalyst.
Palladium on activated carbon catalyzed reductive amination of aldehydes and ketones by triethylsilane
Mirza-Aghayan, Maryam,Tavana, Mahdieh Molaee,Rahimifard, Mahshid,Boukherroub, Rabah
, p. 113 - 115 (2014)
Various aldehydes and ketones were efficiently transformed into the corresponding amines using amine derivatives in the presence of triethylsilane and a catalytic amount of palladium on activated carbon in ethanol. The proposed method provides a one-pot synthesis of various amines in excellent yields after short reaction times.
One-pot reductive amination of aldehydes and ketones using N-methyl-piperidine zinc borohydride (ZBNMPP) as a new reducing agent
Alinezhad, Heshmatollah,Tajbakhsh, Mahmoud,Zamani, Reza
, p. 431 - 434 (2006)
A one-pot reductive amination of aldehydes and ketones using N-methyl piperidine zinc borohydride as a new and stable reducing agent is described. The reaction has been carried out in methanol at room temperature under neutral conditions. Georg Thieme Verlag Stuttgart.
Copper-catalyzed oxygen atom transfer of N-oxides leading to a facile deoxygenation procedure applicable to both heterocyclic and amine N-oxides
Jeong, Jisu,Lee, Donggun,Chang, Sukbok
, p. 7035 - 7038 (2015)
Deoxygenation of various types of N-oxides including both heterocyclic and alkyl(aryl)amine derivatives has successfully been developed by the copper-catalyzed oxygen atom transfer using diazo compounds as the oxygen acceptor. The reaction proceeds smoothly over a broad range of substrates with excellent functional group tolerance under mild conditions. This journal is
