- Copper catalyzed: N-formylation of α-silyl-substituted tertiary N-alkylamines by air
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A site-selective method to prepare N-formyl amines efficiently that relies on the copper(i)-catalyzed oxidation of α-silyl-substituted tertiary N-alkylamines by air at room temperature is described. The oxidative protocol was shown to exhibit excellent functional group tolerance as it was applicable to a wide variety of amine substrates and a number of bioactive molecules and natural products. Moreover, it delinates a ligand-and additive-free amine oxidation process mediated by a low-cost metal salt with oxygen from air taking on the role of both the terminal oxidant and as part of the formylation reagent, which is unprecedented in copper catalysis. It also offers the first synthetic method that can selectively generate α-amino radical species as reactive intermediates from α-silylamines under non-photochemical reaction conditions.
- Bruce, Lachlan David,Chan, Philip Wai Hong,Jin, Jianwen,Xia, Bo,Zhao, Yichao
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supporting information
p. 5296 - 5302
(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 0050; 0051
(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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- 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 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 0061; 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 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 0065; 0066
(2018/05/16)
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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 0064; 0065
(2018/05/16)
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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 0066; 0067
(2018/04/21)
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- Maillard reaction of lactose and fluoxetine hydrochloride a secondary amine
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Analysis of commercially available generic formulations of fluoxetine HCl revealed the presence of lactose as the most common excipient. We show that such formulations are inherently less stable than formulations with starch as the diluent due to the Maillard reaction between the drug, a secondary amine hydrochloride, and lactose. The Amadori rearrangement product was isolated and characterized; the characterization was aided by reduction with sodium borohydride and subsequent characterization of this reduced adduct. The lactose-fluoxetine HCl reaction was examined in aqueous ethanol and in the solid state, in which factors such as water content, lubricant concentration, and temperature were found to influence the degradation. N- Formylfluoxetine was identified as a major product of this Maillard reaction and it is proposed that N-formyl compounds be used as markers for this drug- excipient interaction since they are easy to prepare synthetically. Many characteristic volatile products of the Maillard reaction have been identified by GC/MS, including furaldehyde, maltol, and 2,3-dihydro-3,5- dihydroxy-6-methyl-4H-pyran-4-one. Close similarity between the degradation products of simple mixtures and formulated generic products was found; however, at least one product decomposed at a rate nearly 10 times that predicted from the simple models. Maillard products have also been identified in unstressed capsules. The main conclusions is that drugs which are secondary amines (non just primary amines as sometimes reported) undergo the Maillard reaction with lactose under pharmaceutically relevant conditions. This finding should be considered during the selection of excipients and stability protocols for drugs which are secondary amines or their salts, just as it currently is for primary amines.
- Wirth, David D.,Baertschi, Steven W.,Johnson, Ross A.,Maple, Steven R.,Miller, Marybeth S.,Hallenbeck, Diana K.,Gregg, Stephen M.
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