An Alumino‐Mannich Reaction of Organoaluminum Reagents, Silylated Amines, and Aldehydes

Tarasewicz, Anika; Ensan, Deeba; Batey, Robert A.

doi:10.1002/chem.201801012

Cited by 4 publications

(2 citation statements)

References 39 publications

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“…Subsequently, a transition metal-catalyzed hydrogen transfer or hydrogenation process occurs to yield the desired alkylated amine. With silane as the reducing agent, the generated silylated amine is then hydrolyzed by water to yield the desired amine (step 2) …”

Section: Introductionmentioning

confidence: 99%

Mechanism of Boron-Catalyzed N-Alkylation of Primary and Secondary Arylamines with Ketones Using Silanes under “Wet” Conditions

2018

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Density functional theory (DFT) calculations have been carried out to study the mechanism of N-alkylation of primary and secondary arylamines with aldehydes and ketones under the catalysis of the Lewis acid B(C 6 F 5 ) 3 using silanes. The B(C 6 F 5 ) 3 -mediated reduction of organic substrates is usually reported under anhydrous conditions. It is noteworthy that Ingleson and co-workers have established that B(C 6 F 5 ) 3 could act as a water tolerant catalyst in N-alkylation of arylamines with aldehydes/ketones. Our DFT calculation results revealed that both Lewis acid B(C 6 F 5 ) 3 and water play important roles in the condensation of amine and aldehyde to generate an imine intermediate and in the subsequent reduction of imine to yield an amine product. In the condensation reaction, Brønsted acid B(C 6 F 5 ) 3 -H 2 O acts as the effective catalyst to promote the proton transfer process. The activation free energy barrier is calculated to be 21.1 kcal/ mol, which is 23.0 kcal/mol lower than that of the water-assisted condensation pathway. In the second stage of imine reduction, our DFT studies specifically show that a "one-pot" ionic outer-sphere S N 2@Si transition state is the favorable pathway, featuring the imine hydrate nucleophilically attacking the η 1 -silane boron adduct to activate silane, with an activation free energy barrier of 17.3 kcal/mol. With direct removal of silanol, a subsequent facile hydride transfer from the boronhydride anion [HB(C 6 F 5 ) 3 ] − to the protonated iminium ion generates the alkylated amine product.

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Section: Introductionmentioning

confidence: 99%

Mechanism of Boron-Catalyzed N-Alkylation of Primary and Secondary Arylamines with Ketones Using Silanes under “Wet” Conditions

2018

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“…To the best of our knowledge, the Ni-catalyzed three-component carboalkenylation of 1,3-diene has not been reported . To accomplish the protocol, the alkenylmetallic reagent should be unreactive toward the aldehyde . Additionally, the regio- and stereoselectivity of the proposed three-component reaction is difficult to control.…”

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confidence: 99%

Nickel-Catalyzed Carboalkenylation of 1,3-Dienes with Aldehydes and Alkenylzirconium Reagents: Access to Skipped Dienes

et al. 2021

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A regio- and stereoselective nickel-catalyzed three-component coupling reaction of aldehydes, 1,3-dienes, and alkenylzirconium reagents was realized. The ligand- and additive-free protocol afforded a convenient approach to the synthesis of skipped diene compounds bearing various functionals (e.g., hydroxyl, carbonyl, halide) and heterocyclic groups. The products were readily transformed into structurally diverse polyenes. The utility of this reaction was also demonstrated by the one-pot operation and scale-up preparation.

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Multicomponent Mannich and Related Reactions

Presset,

Le Gall

2024

Reference Module in Chemistry, Molecular Sciences and Chemical Engineering

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An Alumino‐Mannich Reaction of Organoaluminum Reagents, Silylated Amines, and Aldehydes

Cited by 4 publications

References 39 publications

Mechanism of Boron-Catalyzed N-Alkylation of Primary and Secondary Arylamines with Ketones Using Silanes under “Wet” Conditions

Mechanism of Boron-Catalyzed N-Alkylation of Primary and Secondary Arylamines with Ketones Using Silanes under “Wet” Conditions

Nickel-Catalyzed Carboalkenylation of 1,3-Dienes with Aldehydes and Alkenylzirconium Reagents: Access to Skipped Dienes

Multicomponent Mannich and Related Reactions

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