- Tetracoordinate borates as catalysts for reductive formylation of amines with carbon dioxide
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We report sodium trihydroxyaryl borates as the first robust tetracoordinate organoboron catalysts for reductive functionalization of CO2. These catalysts, easily synthesized from condensing boronic acids with metal hydroxides, activate main group element-hydrogen (E-H) bonds efficiently. In contrast to BX3 type boranes, boronic acids and metal-BAr4 salts, under transition metal-free conditions, sodium trihydroxyaryl borates exhibit high reactivity of reductive N-formylation toward a variety of amines (106 examples), including those with functional groups such as ester, olefin, hydroxyl, cyano, nitro, halogen, MeS-, ether groups, etc. The over-performance to catalyze formylation of challenging pyridyl amines affords a promising alternative method to the use of traditional formylation reagents. Mechanistic investigation supports electrostatic interactions as the key for Si/B-H activation, enabling alkali metal borates as versatile catalysts for hydroborylation, hydrosilylation, and reductive formylation/methylation of CO2.
- Du, Chen-Xia,Huang, Zijun,Jiang, Xiaolin,Li, Yuehui,Makha, Mohamed,Wang, Fang,Zhao, Dongmei
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supporting information
p. 5317 - 5324
(2020/09/17)
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- Catalyst-Free Transamidation of Aromatic Amines with Formamide Derivatives and Tertiary Amides with Aliphatic Amines
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A simple catalyst- and promoter-free protocol has been developed for the transamidation of weakly nucleophilic aromatic amines with formamide derivatives and low-reactivity tertiary amides with aliphatic amines. This strategy is advantageous because no catalyst or promoters are needed, no additives are required, separation and purification is easy, and the reaction is scalable. Significantly, this strategy was further applied to synthesize several pharmaceutical molecules on a gram scale, and excellent yields were achieved.
- Yin, Jiawen,Zhang, Jingyu,Cai, Changqun,Deng, Guo-Jun,Gong, Hang
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supporting information
p. 387 - 392
(2019/01/11)
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- Method for preparing formamide derivative by using catalyst-free transamination reaction
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The invention discloses a method for synthesizing a formamide derivative by using a low-reactive catalyst-free and solvent-free tertiary amide and aliphatic amine transamination reaction, wherein thehigh-yield formamide derivative is obtained by directly using N,N-dimethylformamide (DMF) as a formyl source. According to the present invention, the method has advantages of inexpensive and easily available raw materials, inexpensive and easily available acylating reagent, high reaction yield, one-step reaction, low cost, high reaction selectivity, simple operation and the like, and can overcomethe defects of high toxicity of the reaction reagent, requirement of different types of catalysts, high cost, more reaction steps, more by-products and the like in the prior art.
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Paragraph 0046; 0047
(2019/02/13)
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- Mn(II)-Catalyzed N -Acylation of Amines
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A practical protocol has been developed here for the Mn(II)-catalyzed N -acylation of amines with high yields using N, N -dimethylformamide and other amides as the carbonyl source. The protocol is simple, does not require any acid, base, ligand, or other additives, and encompasses a broad substrate scope for primary, secondary, and heterocyclic amines.
- Ma, Juan,Zhang, Jingyu,Gong, Hang
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p. 693 - 703
(2019/01/23)
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- Method for synthesis of formamide derivatives by cobalt catalysis of formylation reaction
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The invention discloses a method for synthesis of formamide derivatives by cobalt catalysis of formylation reaction. The method comprises that the formamide derivatives are produced by one-pot reaction of amine compounds and formamide compounds under the catalysis of cobalt salts; the method has the advantages of cheap and easily obtained reaction raw materials and catalysts, simple reaction stepsand operation, high reaction selectivity, high yield, extendable reaction and the like, and overcomes the defects of high reaction reagent toxicity, expensive catalysts, more reaction steps, more byproducts and the like in the prior art.
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Paragraph 0062; 0063
(2018/04/21)
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- Cobalt(II)-Catalyzed N-Acylation of Amines through a Transamidation Reaction
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A practical protocol has been developed for a Co(OAc)2·4H2O-catalyzed transamidation reaction. The reaction gives high yields and uses N,N-dimethylformamide and other amides as carbonyl sources. The protocol is rapid and simple, and it does not require any acids, bases, ligands, or other additives. It works well for a wide range of primary, secondary, and heterocyclic amines.
- Ma, Juan,Zhang, Feng,Zhang, Jingyu,Gong, Hang
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p. 4940 - 4948
(2018/09/25)
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- Method of using graphene oxide to catalyze formylation reaction to synthesize formamide derivative
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The invention discloses a method of using graphene oxide to catalyze formylation reaction to synthesize a formamide derivative. The method includes: allowing amine compound and formamide compound to be in one-pot reaction under catalytic action of graphene oxide to generate the formamide derivative. Reaction raw materials and a catalyst are low in cost and easy to obtain, the catalyst can be recycled, reaction steps and operations are simple, the method has the advantages of high reaction selectivity, high yield and supportiveness of expanding reaction, and the defects that reaction reagents are high in toxicity, catalysts are expensive, the number of reaction steps is large and the number of byproducts is large in the prior art are overcome.
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Paragraph 0060; 0061
(2018/05/16)
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- N-formylation of amine using graphene oxide as a sole recyclable metal-free carbocatalyst
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Abstract: Graphene oxide (GO), an inexpensive, environment-friendly, and metal-free carbocatalyst, used for the N-formylation of amines is developed. In this reaction, GO shows good activity, selectivity, and recyclability. This strategy has an array of advantages, such as being metal free, without additive, wide-scope protocol, scalable with a low catalyst loading of 3?wt%, use of readily available and recyclable carbocatalyst, and DMF as a readily available formyl source. Furthermore, this strategy provides an avenue for the convenient hydroformylation of various amines. Graphical abstract: [Figure not available: see fulltext.].
- Ma, Juan,Zhang, Jingyu,Zhou, Xiao,Wang, Jiawei,Gong, Hang
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p. 2851 - 2860
(2018/10/31)
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- Method for synthesizing formamide derivative through Mn-catalyzed formylation reaction
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The invention discloses a method for synthesizing a formamide derivative through Mn-catalyzed formylation reaction. The method disclosed by the invention is characterized in that an amine compound anda formamide compound are subjected to one-pot reaction under the catalytic action of manganese salt to generate the formamide derivative. The method disclosed by the invention has the beneficial effects that reaction raw materials and a catalyst are cheap and easy to get, reaction steps and operation are simple, the advantages of high reaction selectivity, high yield and expandable reaction are achieved, and the defects that a reagent is high in toxicity, the catalyst is expensive, reaction steps are tedious and byproducts are more in the prior art are overcome.
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Paragraph 0057; 0058
(2018/05/16)
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- Method for synthesizing formamide derivatives by molybdenum catalyzed formylation reaction
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The invention discloses a method for synthesizing formamide derivatives by molybdenum catalyzed formylation reaction. The method includes that the formamide derivatives are generated by one-pot reaction of amine compounds and formamide compounds under the catalytic action of molybdenum salts and/or molybdenum oxides. Reaction methods and catalysts are cheap and easy to acquire, reaction steps andoperations are simple, the method has advantages of high reaction selectivity, high yield, expandability in reaction and the like, and defects of high toxicity of reaction agents, expensive catalysts,complex reaction steps, high quality of by-products and the like in the prior art are overcome.
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Paragraph 0061; 0062
(2018/05/16)
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- Selective Iron-Catalyzed N-Formylation of Amines using Dihydrogen and Carbon Dioxide
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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.
- Jayarathne, Upul,Hazari, Nilay,Bernskoetter, Wesley H.
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p. 1338 - 1345
(2018/02/14)
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- Oxidation of benzylamines to amides
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A convenient method for the conversion of tertiary benzylamines to benzamides by phase transfer oxidation is described. Yields are good. Regioselectivities are reported.
- Markgraf, J. Hodge,Sangani, Poorab K.,Finkelstein, Manuel
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p. 1285 - 1290
(2007/10/03)
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