367965-70-6Relevant academic research and scientific papers
Polynuclear Enantiopure Salen-Mesoionic Carbene Hybrid Complexes
Schmid, Juliane,Frey, Wolfgang,Peters, René
, p. 4313 - 4324 (2017/11/20)
Salen ligands and mesoionic carbene (MIC) ligands constitute important ligand classes in homogeneous catalysis. In this article we describe the first integration of a salen moiety and MIC donors in the same catalyst entity. Homo- and heterometallic polynuclear metal complexes could be selectively prepared by first installing a metal center (Ni(II), Pd(II)) in the N2O2 salen sphere followed by metalation of the mesoionic carbenes (Ag(I), Pd(II)). The silver complexes could be used for transmetalations to form Au(III) complexes. Several complexes showed catalytic activity in the 1,4-addition of an oxindole to a nitroolefin.
Titanium Salen Complexes with Appended Silver NHC Groups as Nucleophilic Carbene Reservoir for Cooperative Asymmetric Lewis Acid/NHC Catalysis
Latendorf, Katja,Mechler, Melanie,Schamne, Irina,Mack, Daniel,Frey, Wolfgang,Peters, René
, p. 4140 - 4167 (2017/08/07)
Lewis acid catalysis and nucleophilic carbene catalysis are complementary fundamental concepts to accelerate and control chemical reactions of aldehyde substrates. Their efficient merger has recently been achieved using two separate catalyst species. The
Metallosalen-Based Ionic Porous Polymers as Bifunctional Catalysts for the Conversion of CO2 into Valuable Chemicals
Luo, Rongchang,Chen, Yaju,He, Qian,Lin, Xiaowei,Xu, Qihang,He, Xiaohui,Zhang, Wuying,Zhou, Xiantai,Ji, Hongbing
, p. 1526 - 1533 (2017/04/14)
A series of new metallosalen-based ionic porous organic polymers (POPs) were synthesized for the first time using a simple unique strategy based on the free-radical copolymerization reaction. Various techniques were used to characterize the physicochemical properties of these catalysts. These well-designed materials endowed high surface area, hierarchical porous structures, and enhanced CO2/N2 adsorptive selectivity. Moreover, these POPs having both metal centers (Lewis acid) and ionic units (nucleophile) could serve as bifunctional catalysts in the catalytic conversion of CO2 into high value-added chemicals without any additional co-catalyst under mild and solvent-free conditions, for example, CO2/epoxides cycloaddition and Nformylation of amines from CO2 and hydrosilanes. The results demonstrated that the irregular porous structure was very favorable for the diffusion of substrates and products, and the microporous structural property resulted in the enrichment of CO2 near the catalytic centers in the CO2-involved transformations. Additionally, the superhydrophobic property could not only enhance the chemoselectivity of products but also promote the stability and recyclability of catalysts.
METHOD OF PREPARING POLY(ALKYLENE CARBONATE) VIA COPOLYMERIZATION OF CARBON DIOXIDE/EPOXIDE IN THE PRESENCE OF NOVEL COMPLEX
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Paragraph 302 - 305, (2014/10/04)
Provided is a method of preparing poly(alkylene carbonate) using a molecular weight regulator in a process of preparing a copolymer of carbon dioxide/epoxide using a novel complex synthesized from salen-type ligand including a quaternary ammonium salt as a catalyst. According to the present invention, even though the molecular weight regulator is used, an activity of the catalyst may be stably maintained, whereby the low molecular weight of poly(alkylene carbonate) having a desirable level may be effectively provided. In addition, it is expected that since the novel complex as the catalyst of the present invention has a simple structure as compared to the existing copolymerization catalyst, due to the economical preparation cost thereof, the novel complex may be effectively applied to a large-scale commercial process.
Cooperative Al(salen)-pyridinium catalysts for the asymmetric synthesis of trans-configured β-lactones by [2+2]-cyclocondensation of acylbromides and aldehydes: Investigation of pyridinium substituent effects
Meier, Patrick,Broghammer, Florian,Latendorf, Katja,Rauhut, Guntram,Peters, Rene
experimental part, p. 7121 - 7150 (2012/09/07)
The trans-selective catalytic asymmetric formation of β-lactones constitutes an attractive surrogate for anti-aldol additions. Recently, we have reported the first catalyst which is capable of forming trans-β-lactones with high enantioselectivity from aliphatic (and aromatic) aldehyde substrates by cyclocondensation with acyl bromides. In that previous study the concepts of Lewis acid and organic aprotic ion pair catalysis were combined in a salen-type catalyst molecule. Since a pyridinium residue on the salen periphery is essential for high trans- and enantioselectivity, we were interested in the question of whether substituents on the pyridinium rings could be used to further improve the catalyst efficiency, as they might have a significant impact on the effective charges within the heterocycles. In the present study we have thus compared a small library of aluminum salen/bispyridinium catalysts mainly differing in the substituents on the pyridinium residues. As one result of these studies a new catalyst was identified which offers slightly superior stereoselectivity as compared to the previously reported best catalyst. NBO calculations have revealed that the higher stereoselectivity can arguably not be explained by the variation of the effective charge.
Unsymmetric salen ligands bearing a Lewis base: Intramolecularly cooperative catalysis for cyanosilylation of aldehydes
Wen, Ye-Qian,Ren, Wei-Min,Lu, Xiao-Bing
scheme or table, p. 6323 - 6330 (2011/10/09)
A series of unsymmetric salen ligands derived from 1,2-diaminocyclohexane bearing an appended Lewis base on the three-position of one aromatic ring were synthesized by the reaction of various functional salicyaldehydes with the condensation product of 1,2-diaminocyclohexane mono(hydrogen chloride) and 3,5-di-tert-butylsalicylaldehyde. These ligands in conjunction with Ti(O iPr)4 exhibited excellent activity in catalyzing the cyanosilylation of aldehydes with trimethylsilyl cyanide (TMSCN) at mild conditions. The highest activity was observed in the catalyst system with regard to the salen ligand bearing a diethylamino group, which proved to be active even at a high [aldehyde]/[catalyst] ratio up to 50000. In a low catalyst loading of 0.05 mol%, the quantitative conversion of benzaldehyde to the corresponding cyanosilylation product was found within 10 min. at ambient temperature. An intramolecularly cooperative catalysis was proposed wherein the central metal Ti(iv) is suggested to play a role of Lewis acid to activate aldehydes while the appended Lewis base to activate TMSCN.
Mechanistic aspects of the copolymerization of CO2 with epoxides using a thermally stable single-site cobalt(III) catalyst
Ren, Wei-Min,Liu, Zhong-Wen,Wen, Ye-Qian,Zhang, Rong,Lu, Xiao-Bing
supporting information; experimental part, p. 11509 - 11518 (2011/03/21)
The mechanism of the copolymerization of CO2 and epoxides to afford the corresponding polycarbonates catalyzed by a highly active and thermally stable cobalt(III) complex with 1,5,7-triabicyclo[4,4,0] dec-5-ene (designated as TBD, a sterically
Contact ion pair directed Lewis acid catalysis: Asymmetric synthesis of trans-configured β-lactones
Kull, Thomas,Peters, Rene
supporting information; experimental part, p. 5461 - 5464 (2009/03/12)
Opposites attract. A novel concept for dual-activation catalysis takes advantage of the cooperative action of aprotic contact ion pair catalysis and Lewis acid catalysis. This strategy was used for the first trans-selective catalytic asymmetric [2+2] cycl
The one-pot halomethylation of 5-substituted salicylaldehydes as convenient precursors for the preparation of heteroditopic ligands for the binding of metal salts
Wang, Qiang,Wilson, Claire,Blake, Alexander J.,Collinson, Simon R.,Tasker, Peter A.,Schr?der, Martin
, p. 8983 - 8987 (2007/10/03)
The one-pot bromo- and chloro-methylation of various 5-substituted salicylaldehydes with paraformaldehyde and hydrobromic or hydrochloric acid has been achieved. This approach establishes a convenient and flexible method to attach functional arms to salic
