15429-08-0

Upstream product

• 780-25-6 N-benzylidene benzylamine 
• 123-11-5 4-methoxy-benzaldehyde 
• 2393-23-9 4-methoxy-benzylamine 
• 100-51-6 benzyl alcohol 
• 1426958-17-9 N,N-dibenzyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-amine 
• 98-88-4 benzoyl chloride 
• 100-46-9 benzylamine 
• 100-39-0 benzyl bromide 
• 103-49-1 dibenzylamine 
• 55-21-0 benzamide 
• 1485-70-7 N-benzylbenzamide 
• 100-07-2 4-methoxy-benzoyl chloride 
• 105-13-5 4-Methoxybenzyl alcohol 
• 1224452-77-0 dibenzylamine formate 

Relevant academic research and scientific papers

Hydroborative reduction of amides to amines mediated by La(CH2C6H4NMe2-: O)3

The deoxygenative reduction of amides to amines is a great challenge for resonance-stabilized carboxamide moieties, although this synthetic strategy is an attractive approach to access the corresponding amines. La(CH2C6H4NMe2-o)3, a simple and easily accessible lanthanide complex, was found to be highly efficient not only for secondary and tertiary amide reduction, but also for the most challenging primary reduction with pinacolborane. This protocol exhibited good tolerance for many functional groups and heteroatoms, and could be applied to gram-scale synthesis. The active species in this catalytic cycle was likely a lanthanide hydride.

Reduction of Amides to Amines with Pinacolborane Catalyzed by Heterogeneous Lanthanum Catalyst La(CH2C6H4NMe2- o)3@SBA-15

Hydroboration of amides is a useful synthetic strategy to access the corresponding amines. In this contribution, it was found that the supported lanthanum benzyl material La(CH2C6H4NMe2-o)3@SBA-15 was highly active for the hydroboration of primary, secondary, and tertiary amides to amines with pinacolborane. These reactions selectively produced target amines and showed good tolerance for functional groups such as -NO2, -halogen, and -CN, as well as heteroatoms such as S and O. This reduction procedure exhibited the recyclable and reusable property of heterogeneous catalysts and was applicable to gram-scale synthesis. The reaction mechanisms were proposed based on some control experiments and the previous literature. This is the first example of hydroborative reduction of amides to amines mediated by heterogeneous catalysts.

Homoleptic Bis(trimethylsilyl)amides of Yttrium Complexes Catalyzed Hydroboration Reduction of Amides to Amines

Homoleptic lanthanide complex Y[N(TMS)2]3 is an efficient homogeneous catalyst for the hydroboration reduction of secondary amides and tertiary amides to corresponding amines. A series of amides containing different functional groups such as cyano, nitro, and vinyl groups were found to be well-tolerated. This transformation has also been nicely applied to the synthesis of indoles and piribedil. Detailed isotopic labeling experiments, control experiments, and kinetic studies provided cumulative evidence to elucidate the reaction mechanism.

Method for synthesizing tertiary amine derivative by catalyzing hydroboration reaction of tertiary amide by rare earth

The invention discloses a method for synthesizing a tertiary amine derivative by catalyzing a hydroboration reaction of tertiary amide by rare earth. Under the protection of nitrogen, in a rare earthcatalysis system, the tertiary amine derivative is prepared through a hydrogen transfer reduction reaction catalyzed by rare earth with tertiary amide and pinacol borane as raw materials. The method has the advantages and effects that a novel synthesis process is utilized, and the tertiary amine derivative prepared by using the method disclosed by the invention is high in quality and stable in process; the raw materials are widely sourced or easy to prepare and store, and the reaction yield is high; and in addition, a catalyst can be directly commercially purchased or is easily, directly and simply synthesized, and can be used in actual production.

Iridium-Catalyzed Alkylation of Amine and Nitrobenzene with Alcohol to Tertiary Amine under Base- and Solvent-Free Conditions

Herein, an efficient and green method for the selective synthesis of tertiary amines has been developed that involves iridium-catalyzed alkylation of various primary amines with aromatic or aliphatic alcohols. Notably, the catalytic protocol enables this transformation in the absence of additional base and solvent. Furthermore, the alkylation of nitrobenzene with primary alcohol to tertiary amine has also been achieved by the same catalytic system. Deuterium-labeling experiments and a series of control experiments were conducted, and the results suggested that an intermolecular borrowing hydrogen pathway might exist in the alkylation process.

Hydrosilylative Reduction of Tertiary Amides to Amines Catalyzed by N-(Phosphinoaryl)anilido Complexes of Iron and Cobalt

The synthesis and structural characterization of low-coordinate Fe(II) and Co(II) complexes supported by the monoanionic P,N-ligand N-(2-dicyclohexylphosphinophenyl)-2,6-diisopropylanilide are described. A three-coordinate (P,N)Fe-hexamethyldisilazide complex (2), and four-coordinate (P,N)Fe- (3-Fe) and (P,N)Co-alkyl (3-Co) complexes were evaluated as pre-catalysts for the hydrosilylative reduction of amides with PhSiH3 (5 mol % pre-catalyst, 1 equiv. PhSiH3, 80 °C, 1–24 h). The Fe complex 2 proved to be more broadly effective for the reduction of a variety of tertiary amide substrates, and was shown to mediate the reduction of N,N-dibenzylbenzamide at a loading of 1 mol %, to achieve near quantitative formation of tribenzylamine in 1 h (80 °C). Complex 2 also proved effective for the hydrosilylation of tertiary amides under ambient conditions (5 mol % Fe, 24 h), which is a unique example of room temperature amide hydrosilylation mediated by an Fe catalyst without the need for photochemical activation. Given the widespread use of amide reduction protocols in synthesis, the development of efficient Fe-based catalysts that operate under mild conditions is an important target.

A Manganese Pre-Catalyst: Mild Reduction of Amides, Ketones, Aldehydes, and Esters

A new (N-phosphinoamidinate)manganese complex is shown to be a useful pre-catalyst for the hydrosilative reduction of carbonyl compounds, and in most cases at room temperature. The Mn-catalyzed reduction of tertiary amides to tertiary amines, with a useful scope, is demonstrated for the first time by use of this catalyst, and is competitive with the most effective transition-metal catalysts known for such transformations. Ketones, aldehydes, and esters were also successfully reduced under mild conditions by using this new Mn catalyst.

Efficient and Selective Hydrosilylation of Secondary and Tertiary Amides Catalyzed by an Iridium(III) Metallacycle: Development and Mechanistic Investigation

Readily accessible cationic IrIII metallacycles catalyze efficiently the chemoselective hydrosilylation of tertiary and secondary amides to amines. The catalyst described herein operates at low loadings using inexpensive 1,1,3,3-tetramethyldisiloxane and allows fast reactions with high yields, selectivities, and turnover numbers. A transient iminium intermediate has been observed for the first time by using mass spectrometry, and the activation of the catalyst and the silane reagent have been studied by using DFT calculations. These fundamental insights support the present and future improvements of IrIII metallacycles through proper ligand modifications and enable further broad applications of catalysts based on metallacycles.

Simple Metal-Free Direct Reductive Amination Using Hydrosilatrane to Form Secondary and Tertiary Amines

This work describes the use of cheap, safe, and easy-to-handle hydrosilatrane as the reductant in direct reductive amination reactions. This efficient method enables a facile, metal-free access to secondary and tertiary amines from a wide range of aldehydes and ketones, with the synthesis of tertiary amines requiring no additives at all. This reaction demonstrates excellent functional group tolerance, chemoselectivity, and scalability. (Figure presented.).

Cs2CO3-Promoted Direct N-Alkylation: Highly Chemoselective Synthesis of N-Alkylated Benzylamines and Anilines

Herein is described an efficient and chemoselective method for the synthesis of diversely substituted secondary amines in yields up to 98 %. Direct mono-N-alkylation of primary benzylamines and anilines with a wide range of alkyl halides is promoted by a cesium base in the absence of any additive or catalyst. The basicity and solubility of cesium carbonate in anhydrous N,N-dimethylformamide not only enables mono-N-alkylation of primary amines but also suppresses undesired dialkylation of the desired amines.