172027-15-5Relevant articles and documents
Chemoselective heterogeneous iridium catalyzed hydrogenation of cinnamalaniline
Savela, Risto,Shcherban, Nataliya D.,Melander, Marko M.,Bezverkhyy, Igor,Simakova, Irina L.,L?ngvik, Otto,Kholkina, Ekaterina,Schindler, Tamara,Krauβ, Annabelle,Honkala, Karoliina,Murzin, Dmitry Yu.,Leino, Reko
, p. 1481 - 1496 (2021)
Selective hydrogenation of unsaturated imines over heterogeneous catalysts is an ecologically feasible and effective way to produce commercially valuable saturated imines and unsaturated amines under mild conditions, avoiding the utilization of toxic halides. The liquid-phase hydrogenation of a model imine, cinnamalaniline, over Ir, Ru, Pd and Au catalysts was studied in polar protic (methanol, 2-propanol), polar aprotic (methyltert-butyl ether) and non-polar aprotic (toluene) solvents at 40-80 °C under atmospheric hydrogen pressure. Different metal oxides (Al2O3, ZrO2, SiO2) and carbon composites based on carbon nitrides synthesized by pyrolysis of ethylenediamine or melamine modified by KOH, HNO3, NH4Cl or TEOS (including template KIT-6), porous carbon (samples prepared by pyrolysis of sucrose, including template KIT-6) and mesoporous carbon Sibunit were applied to study the effect of the support. Among the tested metals, iridium exhibited the most promising catalytic performance in terms of hydrogenation activity and chemoselectivity towards unsaturated amine. The use of Ir on carbon nitrides (C3N4-NH4Cl, CxNy-KIT-6) and amphoteric metal oxides (ZrO2, Al2O3) in nonpolar aprotic toluene solvent provided the best selectivity towards unsaturated amine by minimizing oligomerization. Computational studies indicate that the selective hydrogenation of the CN group on Ir results from a favorable cinnamalaniline adsorption geometry at high surface coverage. Comparable heterogeneously catalyzed highly chemoselective hydrogenation of unsaturated imine into unsaturated amine under atmospheric hydrogen pressure and low temperatures has not been reported previously.
First efficient two-step/one-pot zirconium (IV)isopropoxide-mediated reductive amination of carbonyl compounds
Pieri, Cyril,Brunel, Jean Michel
, p. 448 - 456 (2015/06/22)
An efficient method for the synthesis of various primary and secondary amines through a zirconium(IV) isopropoxide-mediated reductive amination reaction of aldehydes and ketones is reported. A series of different aldehydes, ketones and amines were used leading to the expected amino products in moderate to excellent yields. The mechanistic rationale of this reaction has been postulated through the formation of a transient imine species and a diastereoselective version using (R)-phenylethylamine as chiral inducer led to the expected products in moderate to excellent yields and with diastereoselectivities up to 100%.
Highly efficient iron phthalocyanine catalyzed oxidative synthesis of imines from alcohols and amines
Bala, Manju,Verma, Praveen Kumar,Kumar, Neeraj,Sharma, Upendra,Singh, Bikram
supporting information, p. 732 - 737 (2013/08/23)
An efficient iron phthalocyanine catalyzed method was developed for direct oxidative coupling of alcohols with amines to afford corresponding imines. The present protocol is applicable to various substituted aromatic and aliphatic alcohols and amines. The reaction is believed to proceed via activation of alcohols by iron phthalocyanines through Lewis acid-base interaction to form aldehydes, which by nucleophilic attack of amines are converted into the corresponding imines.
Electrochemical allylation reactions of simple imines in aqueous solution mediated by nanoscale zinc architectures
Huang, Jing-Mei,Wang, Xu-Xiao,Dong, Yi
supporting information; experimental part, p. 924 - 927 (2011/03/20)
I zinc we're alone now: The title reactions were achieved in an undivided cell fitted with a pair of zinc electrodes in aqueous solution. A preliminary study on the relationship of reaction activity and surface morphology showed that the deposited zinc powders with nanoscale architectures had very high activity.
Vanadium(I) chloride and lithium vanadium(I) dihydride as selective epimetallating reagents for π- and σ-bonded organic substrates
Eisch, John J.,Fregene, Paul O.
scheme or table, p. 4482 - 4492 (2009/05/07)
Subvalent vanadium(I) salts, of empirical formulas, VCl, vanadium(I) chloride and LiVH2, lithium vanadium(I) dihydride, whose efficient preparation, structural constitution and mode of reaction toward certain organic substrates have been described in a preceding article, are here evaluated in their reactions toward a wide variety of π- and σ-bonded organic substrates, namely carbonyl, imine, azo, alkene, 1,3-diene, nitrile π-bonds and C-X, C-O, C-N and N-N σ-bonds. Compared with the high reactivity of CrCl and LiCrH2 reagents in attacking both types of bonds, the VCl and LiVH2 reagents were much milder and selective in epimetallating π-bonds, often forming the 1:1 adduct of LiVH2 and π-bonded substrate as the major product. Finally, the vanadium reagents showed little tendency to cleave C-O, C-S and C-N bonds and a smaller scope in cleaving C-X bonds than their chromium counterparts. Because of their selectivity these vanadium reagents offer the following preparative promise: 1) smooth McMurry carbonyl coupling to their reductive dimers; 2) deoxygenation of epoxides; 3) selective aromatic C-X reduction; 4) high yields of epimetallated carbonyls or imines as intermediates to α-hydroxy and α-amino acids; 5) 1,4-reductions of 1,3-alkadienes; 6) reductive dimerization of nitriles to ketones; 7) 1,4 or 1,n-epimetallations leading to acyloins or indoles; and 8) reductive dimerizations of azines to produce unusual imidazole derivatives. In explaining the greater kinetic stability of the 1:1 LiVH2 adduct with carbonyl or imine substrates it is pointed out that such epimetallated adducts from LiVH2 would likely be diamagnetic, whereas such adducts from LiCrH2 have an unpaired electron on the Cr center and hence would rupture, so that the electron would be on the C center. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
Recyclable polymeric π-acid catalyst effective on Mannich-type reaction in water
Masaki, Yukio,Yamazaki, Kouichi,Kawai, Hyouei,Yamada, Tomoyasu,Itoh, Akichika,Arai, Yoshitsugu,Furukawa, Hiroshi
, p. 591 - 593 (2007/10/03)
Polymer-supported dicyanoketene acetal (poly-DCKA-1), synthesized by copolymerization of a DCKA bearing a 4-vinylbenzyl group with ethyleneglycol dimethacrylate, was found to be an excellent recyclable catalyst for the three-component Mannich-type reaction of aldehydes, aromatic amines, and TMS enolate of ethyl isobutyrate in water as the sole solvent.
The addition of amines to diisobutylaluminum-imine complexes. Preparation of NPS R-568 hydrochloride
Barmore, Robert M.,Logan, Sarah R.,Van Wagenen, Bradford C.
, p. 3451 - 3454 (2007/10/03)
A facile procedure for the preparation of secondary and tertiary amines from nitriles has been developed. The addition of amines to diisobutylaluminum-imine complexes derived by treating nitriles with DIBAL-H was found to proceed in moderate to good yield
