234449-91-3Relevant articles and documents
Palladium-catalyzed carbonylation of aryl bromides using microwave heating and bis[CP-Fe(II)-(CO)2] as a carbon monoxide source
Roy, Tamal,Rydfjord, Jonas,S?vmarker, Jonas,Nordeman, Patrik
, p. 1230 - 1232 (2018)
A palladium-catalyzed, microwave assisted carbonylative reaction is described for the synthesis of benzamides from aryl bromides and primary or secondary amines. The developed method uses bis(cyclopentadienyldicarbonyliron) as a solid source of carbon monoxide to produce a diverse set of secondary and tertiary amides in 42–82% yield.
Addition of organostannanes to isocyanate catalyzed by a rhodium complex
Koike, Tooru,Takahashi, Masabumi,Arai, Nobumichi,Mori, Atsunori
, p. 1364 - 1365 (2004)
Arylstannanes add to isocyanate in the presence of a rhodium catalyst to afford amides in good to excellent yields. Use of a phenol derivative as an additive is found to play an essential role for the successful reaction.
Zirconium Oxide-Catalyzed Direct Amidation of Unactivated Esters under Continuous-Flow Conditions
Rashed, Md. Nurnobi,Masuda, Koichiro,Ichitsuka, Tomohiro,Koumura, Nagatoshi,Sato, Kazuhiko,Kobayashi, Shū
, p. 2529 - 2535 (2021/02/01)
A sustainable and environmentally benign direct amidation reaction of unactivated esters with amines has been developed in a continuous-flow system. A commercially available amorphous zirconium oxide was found to be an efficient catalyst for this reaction. While the typical amidation of esters with amines requires a stoichiometric amount of a promoter or metal activator, the present continuous-flow method enabled the direct amidation reaction under additive-free conditions with an extensive diversity towards various functional groups. High yields of the products were obtained with a nearly equimolar proportion of starting materials to reduce byproduct formation, which renders this process applicable for use in a sequential-flow system. (Figure presented.).
Carboxyboronate as a Versatile In Situ CO Surrogate in Palladium-Catalyzed Carbonylative Transformations
Tien, Chieh-Hung,Trofimova, Alina,Holownia, Aleksandra,Kwak, Branden S.,Larson, Reed T.,Yudin, Andrei K.
supporting information, p. 4342 - 4349 (2020/12/25)
The application of carboxy-MIDA-boronate (MIDA=N-methyliminodiacetic acid) as an in situ CO surrogate for various palladium-catalyzed transformations is described. Carboxy-MIDA-boronate was previously shown to be a bench-stable boron-containing building block for the synthesis of borylated heterocycles. The present study demonstrates that, in addition to its utility as a precursor to heterocycle synthesis, carboxy-MIDA-boronate is an excellent in situ CO surrogate that is tolerant of reactive functionalities such as amines, alcohols, and carbon-based nucleophiles. Its wide functional-group compatibility is highlighted in the palladium-catalyzed aminocarbonylation, alkoxycarbonylation, carbonylative Sonogashira coupling, and carbonylative Suzuki–Miyaura coupling of aryl halides. A variety of amides, esters, (hetero)aromatic ynones, and bis(hetero)aryl ketones were synthesized in good-to-excellent yields in a one-pot fashion.
Application of phase-vanishing method with CO gas evolution to carbonylation reactions
Adachi, Yusuke,Matsubara, Hiroshi
, p. 89 - 95 (2018/10/26)
Although carbon monoxide (CO) is considered a practical source of the carbonyl functionality in various compounds, handling CO gas is difficult. The phase-vanishing (PV) method, using highly fluorinated solvents as the phase screen, was thus employed, in which CO was evolved for use in organic synthesis. An H-shaped reactor bearing two reaction chambers was employed. In the first chamber, CO was efficiently generated from sulfuric acid and ammonium formate under the PV conditions, and then consumed in the second chamber in a range of palladium-catalysed carbonylation reactions, affording the desired products. Use of this PV system allowed for easy and safe generation of hazardous CO gas, and its use thereof in organic synthesis.
Tunable Ligand Effects on Ruthenium Catalyst Activity for Selectively Preparing Imines or Amides by Dehydrogenative Coupling Reactions of Alcohols and Amines
Higuchi, Takafumi,Tagawa, Risa,Iimuro, Atsuhiro,Akiyama, Shoko,Nagae, Haruki,Mashima, Kazushi
supporting information, p. 12795 - 12804 (2017/09/06)
Selective dehydrogenative synthesis of imines from a variety of alcohols and amines was developed by using the ruthenium complex [RuCl2(dppea)2] (6 a: dppea=2-diphenylphosphino-ethylamine) in the presence of catalytic amounts of Zn(OCOCF3)2 and KOtBu, whereas the selective dehydrogenative formation of amides from the same sources was achieved by using another ruthenium complex, [RuCl2{(S)-dppmp}2] [6 d: (S)-dppmp=(S)-2-((diphenylphosphenyl)methyl)pyrrolidine], in the presence of catalytic amounts of Zn(OCOCF3)2 and potassium bis(trimethylsilyl)amide (KHMDS). Our previously reported ruthenium complex, [Ru(OCOCF3)2(dppea)2] (8 a), was the catalyst precursor for the imine synthesis, whereas [Ru(OCOCF3)2{(S)-dppmp}2] (8 d), which was derived from the treatment of 6 d with Zn(OCOCF3)2 and characterized by single-crystal X-ray analysis, was the pre-catalyst for the amide formation. Control experiments revealed that the zinc salt functioned as a reagent for replacing chloride anions with trifluoroacetate anions. Plausible mechanisms for both selective dehydrogenative coupling reactions are proposed based on a time-course study, Hammett plot, and deuterium-labeling experiments.
AIBN-initiated metal free amidation of aldehydes using N-chloroamines
Vanjari, Rajeshwer,Guntreddi, Tirumaleswararao,Singh, Krishna Nand
, p. 351 - 356 (2014/01/06)
An efficient and environmentally benign amidation of aldehydes with N-chloroamines has been developed using AIBN as an initiator. This methodology offers a metal free and base free approach and is endowed with mild reaction conditions, high yields, and good functional group tolerance.
Amide synthesis from alcohols and amines catalyzed by a RuII-N-heterocyclic carbene (NHC)-carbonyl complex
Saha, Biswajit,Sengupta, Gargi,Sarbajna, Abir,Dutta, Indranil,Bera, Jitendra K.
, p. 124 - 130 (2014/12/11)
Treatment of [Ru2(CO)4(CH3CN)6](BF4)2 with 3-methyl-1-(pyridin-2-yl)-imidazolium bromide in the presence of tetrabutylammonium bromide at room temperature in dichloromethane affords a RuII-N-heterocyclic carbene-carbonyl complex [Ru(py-NHC)(CO)2Br2] (1). Catalyst 1 displays diverse substrate scope for phosphine-free acceptorless coupling between alcohols and amines to amides at low catalyst loading. A RuII-dihydride/Ru0 sequence is proposed in the catalytic cycle.
Mesoporous niobium oxide spheres as an effective catalyst for the transamidation of primary amides with amines
Ghosh, Subhash Chandra,Li, Cheng Chao,Zeng, Hua Chun,Ngiam, Joyce S. Y.,Seayad, Abdul M.,Chen, Anqi
, p. 475 - 484 (2014/05/20)
Mesoporous niobium oxide spheres (MNOS), conveniently prepared by a novel antisolvent precipitation approach, have been shown to be an effective catalyst for the transamidation of primary amides with amines. This novel transamidation can be efficiently carried out under solvent-free conditions and is applicable to a wide range of primary amides and amines to provide N-alkyl amides in good to excellent yields. The catalyst is highly stable and reusable. The application of this transamidation reaction has been demonstrated in the synthesis of antidepressant drug moclobemide and other druglike compounds.
Mechanistic investigation of the one-pot formation of amides by oxidative coupling of alcohols with amines in methanol
Mielby, Jerrik,Riisager, Anders,Fristrup, Peter,Kegn?s, S?ren
, p. 211 - 216 (2013/08/24)
The one-pot formation of amides by oxidative coupling of alcohols and amines via intermediate formation of methyl ester using supported gold and base as catalysts was studied using the Hammett methodology. Determining the relative reactivity of four different para-substituted benzyl alcohol derivatives showed that the first step of the reaction generates a partial positive charge in the benzylic position (i.e. by hydride abstraction), while the second step of the reaction builds up negative charge in the rate determining step. The aminolysis of the methyl ester intermediate was further investigated by means of DFT/B3LYP. The transition state structures and energies were determined for both a concerted and a neutral two-step reaction mechanism. As expected, the base-promoted two-step mechanism was found to be the most energetically favourable and this reaction mechanism was used to construct a theoretical Hammett plot that was in good agreement with the one obtained experimentally.
