Glycerol Upgrading via Hydrogen Borrowing: Direct Ruthenium-Catalyzed Amination of the Glycerol Derivative Solketal

Stålsmeden, Anna Said; Belmonte‐Vázquez, José L.; Weerdenburg, Kim van; Rae, Rebecca; Norrby, Per‐Ola; Kann, Nina

doi:10.1021/acssuschemeng.6b01659

Cited by 26 publications

(13 citation statements)

References 64 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Based on prior art, a selection of phosphine ligands illustrated in Figure were tested. Results from the ligand screening are summarized in Table .…”

Section: Resultsmentioning

confidence: 99%

“…In recent years, various homogeneous and heterogeneous catalytic methods have emerged in the borrowing hydrogen field. For homogeneous applications, different transition metal catalysts based on iridium, copper, nickel, iron, cobalt, manganese, rhodium and ruthenium have been employed. Especially the ruthenium‐based systems have been widely and successfully applied to a large variety of amines and nitriles…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Ruthenium Catalyzed N‐Alkylation of Cyclic Amines with Primary Alcohols

2020

View full text Add to dashboard Cite

A robust alcohol amination protocol using common saturated amines and primary alcohols as starting materials is described. The reactions are catalyzed by combination of dichloro(p-cymene)ruthenium(II) dimer precatalyst with triphenylphosphine ligand, with the excess alcohol substrate or toluene [a] Dr.amines. An important secondary goal was to minimize the waste produced in the purification of the products, i.e., simple removal of catalyst complex and purification of products without the need of chromatographic separation. Here, we describe a robust triphenylphosphine ligated dichloro(p-cymene)ruthenium(II) dimer catalyzed methodology for alkylation of cyclic amines with primary alcohols, while simultaneously minimizing the necessary purification operations. Results and DiscussionThe N-alkylation of morpholine with 1-butanol, illustrated in Scheme 2, was selected as a model reaction, based on the good availability of the reactants. This allowed the reactions to be performed at close to one gram scale in the preliminary screening, carried out in stainless steel reactors at elevated pressure and temperature. Scheme 2. N-Alkylation of morpholine with 1-butanol using dichloro(p-cymene)ruthenium(II) dimer precatalyst in combination with phosphine ligands.Based on prior art, [16][17][18]20] a selection of phosphine ligands illustrated in Figure 2 were tested. Results from the ligand screening are summarized in Table 1. As expected, the bidentate ligands DPPF, DPPB and DPEphos in combination with dichloro(p-cymene)ruthenium(II) dimer provided good results even at 0.13 mol-% catalyst loading within 21 hours (Table 1, Entries 4, 15 and 17). Tridentate Triphos ligand provided acceptable results in the same reaction setting (Table 1, Entry 21). Also, a number of monodentate ligands, cataCXium®PCy, triphenylphosphine (Ph 3 P) and methoxy derivatized triphenylphosphines were investigated. All monodentate ligands resulted in relatively poor GC-based yields for N-butyl morpholine, or in no reaction at all. In cases of bidentate ligands, having excess of ligand to ruthenium center (above 1:1 ratio) had minimal to no benefits with respect to the overall yield of N-butyl Figure 2. Ligands used in the reaction screening.

show abstract

“…Based on prior art, a selection of phosphine ligands illustrated in Figure were tested. Results from the ligand screening are summarized in Table .…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Ruthenium Catalyzed N‐Alkylation of Cyclic Amines with Primary Alcohols

2020

View full text Add to dashboard Cite

show abstract

“…Reaction pathways according to the time courses. À CO]; and a tiny band centred at 2133-2141 cm À 1 , which is usually considered to be the signal of tricarbonyl species on partially oxidized Ru [Ru n + À (CO) 3 ]. [16] Again, we did not find significant difference of the location of CO over Ru species in all three catalysts, in consistence with XPS results.…”

Section: Resultsmentioning

confidence: 99%

“…Amines are important compounds in natural products and medicines, and are irreplaceable intermediates in the synthesis of fine chemicals, including dyes, pesticide and herbicide . Generally, there are three typical amination approaches: amination of halides,hydrogen‐borrowing amination of alcohol or phenol,and the reductive amination of ketone or aldehyde . The reaction from halides to amines has been well established .…”

Section: Introductionmentioning

confidence: 99%

Morphology‐Tuned Activity of Ru/Nb₂O₅ Catalysts for Ketone Reductive Amination

et al. 2019

View full text Add to dashboard Cite

Amines are important compounds in natural products and medicines. Specifically, cyclopentylamine is one of the value‐added chemicals widely used in the production of pesticides, cosmetics and medicines. In this work, three Ru/Nb2O5 catalysts with different Nb2O5 morphologies were used in the reductive amination of cyclopentanone under mild reaction conditions (90 °C, 2 MPa H2), among which 1 %Ru/Nb2O5−L catalyst exhibits best performance with the yield of cyclopentylamine reaching 84 %. This catalytic system is stable and has not significant deactivation even after 5 runs in the durability test. In addition, this catalyst can be extended to a series of aldehydes/ketones. Further comprehensive characterizations (XPS analysis and CO‐adsorption DRIFT) reveal that the electronic effect of Ru species can be ruled out; instead, the activity of the catalyst is strongly influenced by the geometric effect. Layered Nb2O5 material possesses the highest surface area, resulting in the highest Ru dispersion, and therefore shows the highest catalytic activity. The in‐situ DRIFT‐MS technique was also used to reveal and understand the reaction mechanism. It is found that Ru species play a key role in activating carbonyl groups. This study illustrates a promising application of Ru/Nb2O5‐Layer catalyst in the synthesis of amine and provides an understanding to the reaction mechanism.

show abstract

“…2015 年 Shafir 等 [46] 对 Moasser 等的反应条件进行了 N-烷基取代的丙三醇衍生物在有机合成中具有广泛的应用前景 [52] . Kann 等 [53] 报道了丙三醇衍生物和仲胺为原料在 RuCl 2 (cymene) 2 /dpePhos 或 dppf 催化体系中, 在甲苯或叔丁醇中加热至 130 ℃左右, 得到 C-N 偶联的产物, 收率 64%～97%. 在该催化体系, 他们对镇咳药羟苯哌嗪的中间体进行了合成, 收率 86%.…”

unclassified