180207-85-6Relevant articles and documents
Selective Iron-Catalyzed N-Formylation of Amines using Dihydrogen and Carbon Dioxide
Jayarathne, Upul,Hazari, Nilay,Bernskoetter, Wesley H.
, p. 1338 - 1345 (2018/02/14)
A family of iron(II) carbonyl hydride species supported by PNP pincer ligands was identified as highly productive catalysts for the N-formylation of amines via CO2 hydrogenation. Specifically, iron complexes supported by two different types of PNP ligands were examined for formamide production. Complexes containing a PNP ligand with a tertiary amine afforded superior turnover numbers in comparison to complexes containing a bifunctional PNP ligand with a secondary amine, indicating that bifunctional motifs are not required for catalysis. Systems incorporating a tertiary amine containing a PNP ligand were active for the N-formylation of a variety of amine substrates, achieving TONs up to 8900 and conversions as high as 92%. Mechanistic experiments suggest that N-formylation occurs via an initial, reversible reduction of CO2 to ammonium formate followed by dehydration to produce formamide. Several intermediates relevant to this reaction pathway, as well as iron-containing deactivation species, were isolated and characterized.
Manganese-Catalyzed N-Formylation of Amines by Methanol Liberating H2: A Catalytic and Mechanistic Study
Chakraborty, Subrata,Gellrich, Urs,Diskin-Posner, Yael,Leitus, Gregory,Avram, Liat,Milstein, David
supporting information, p. 4229 - 4233 (2017/04/04)
The first example of a base metal (manganese) catalyzed acceptorless dehydrogenative coupling of methanol and amines to form formamides is reported herein. The novel pincer complex (iPr-PNHP)Mn(H)(CO)2 catalyzes the reaction under mild conditions in the absence of any additives, bases, or hydrogen acceptors. Mechanistic insight based on the observation of an intermediate and DFT calculations is also provided.
MANGANESE BASED COMPLEXES AND USES THEREOF FOR HOMOGENEOUS CATALYSIS
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Paragraph 00406; 00407, (2017/09/05)
The present invention relates to novel manganese complexes and their use, inter alia, for homogeneous catalysis in (1) the preparation of imine by dehydrogenative coupling of an alcohol and amine; (2) C-C coupling in Michael addition reaction using nitriles as Michael donors; (3) dehydrogenative coupling of alcohols to give esters and hydrogen gas (4) hydrogenation of esters to form alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di- lactones), or polyesters); (5) hydrogenation of amides (including cyclic dipeptides, lactams, diamide, polypeptides and polyamides) to alcohols and amines (or diamine); (6) hydrogenation of organic carbonates (including polycarbonates) to alcohols or hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (7) dehydrogenation of secondary alcohols to ketones; (8) amidation of esters (i.e., synthesis of amides from esters and amines); (9) acylation of alcohols using esters; (10) coupling of alcohols with water and a base to form carboxylic acids; and (11) preparation of amino acids or their salts by coupling of amino alcohols with water and a base. (12) preparation of amides (including formamides, cyclic dipeptides, diamide, lactams, polypeptides and polyamides) by dehydrogenative coupling of alcohols and amines; (13) preparation of imides from diols.
Synthesis of pyrrolidones and quinolines from the known biomass feedstock levulinic acid and amines
Ortiz-Cervantes, Carmen,Flores-Alamo, Marcos,García, Juventino J.
supporting information, p. 766 - 771 (2016/02/05)
The catalytic conversion of biomass-derived compounds into value-added products such as food additives, agrochemical components, and pharmaceutical formulations, is a promising and cost effective synthetic strategy. Here, we describe the synthesis of a variety of N-(alkyl, aryl)-5-methyl-2-pyrrolidones through the reductive amination of levulinic acid using formic acid as the hydrogen source. This system is catalyzed by 3.8 nm ruthenium nanoparticles that were prepared by thermal decomposition of [Ru3(CO)12] in solvent-free conditions. When the reactions were carried out without the catalyst, the pyrrolidones were obtained with low yield and poor selectivity. In addition, the reaction between levulinic acid and 2-ethynylaniline produced 2-(2,4-dimethylquinolin-3-yl) acetic acid (8) in mild and metal-free conditions with good yield. Furthermore, the synthesis of substituted quinolines was achieved through a condensation reaction between levulinic acid and different 2-alkynylanilines promoted by p-toluenesulfonic acid, this method is highlighted as a novel procedure for the preparation of quinolines.
Leuckart-Wallach Route Toward Isocyanides and Some Applications
Neochoritis, Constantinos G.,Zarganes-Tzitzikas, Tryfon,Stotani, Silvia,D?mling, Adrian,Herdtweck, Eberhardt,Khoury, Kareem,D?mling, Alexander
supporting information, p. 493 - 499 (2015/09/22)
Isocyanide-based multicomponent reactions (IMCR) are among the most important chemical reactions to efficiently generate molecular diversity and have found widespread use in industry and academia. Generally, isocyanides are synthesized in 1-2 steps starting from primary amines. Here, we provide experimental detail on an alternative approach toward formamides and, thus, isocyanides via the Leuckart-Wallach reaction in an improved variation. The resulting >50 synthesized and characterized formamides are useful starting materials for IMCR, as well as other chemistries. The advantage of using the Leuckart-Wallach pathway to formamides and isocyanides is the lower price, on average, of the starting materials, as well as their differential and complementary structural diversity, as compared to the primary amine pathway.
C-N and N-H Bond Metathesis Reactions Mediated by Carbon Dioxide
Wang, Yehong,Zhang, Jian,Liu, Jing,Zhang, Chaofeng,Zhang, Zhixin,Xu, Jie,Xu, Shutao,Wang, Fangjun,Wang, Feng
, p. 2066 - 2072 (2015/06/30)
Herein, we report CO2-mediated metathesis reactions between amines and DMF to synthesize formamides. More than 20 amines, including primary, secondary, aromatic, and heterocyclic amines, diamines, and amino acids, are converted to the corresponding formamides with good-to-excellent conversions and selectivities under mild conditions. This strategy employs CO2 as a mediator to activate the amine under metal-free conditions. The experimental data and in situ NMR and attenuated total reflectance IR spectroscopy measurements support the formation of the N-carbamic acid as an intermediate through the weak acid-base interaction between CO2 and the amine. The metathesis reaction is driven by the formation of a stable carbamate, and a reaction mechanism is proposed.
Catalytic enantioselective Michael addition of α-aryl-α- isocyanoacetates to vinyl selenone: Synthesis of α,α-disubstituted α-amino acids and (+)- and (-)-trigonoliimine A
Buyck, Thomas,Wang, Qian,Zhu, Jieping
supporting information, p. 12714 - 12718 (2013/12/04)
Be like Mike: The title reaction in the presence of the catalyst 1 afforded Michael adducts in excellent yields and enantioselectivities. The adducts were readily converted into α,α′-disubstituted α-amino acids. The enantioselective total synthesis of bot
3-Phenyl-substituted imidazo[1,5-a]quinoxalin-4-ones and imidazo[1,5- a]quinoxaline ureas that have high affinity at the GABA(A)/benzodiazepine receptor complex
Jacobsen, E. Jon,Stelzer, Lindsay S.,Belonga, Kenneth L.,Carter, Donald B.,Im, Wha Bin,Sethy, Vimala H.,Tang, Andrew H.,Von Voigtlander, Philip F.,Petke, James D.
, p. 3820 - 3836 (2007/10/03)
A series of imidazo[1,5-a]quinoxalin-4-ones and imidazo[1,5- a]quinoxaline ureas containing substituted phenyl groups at the 3-position was developed. Compounds within the imidazo-[1,5-a]quinoxaline urea series had high affinity for the GABA(A)/benzodiaze
