P(III)/P(V)-Catalyzed Methylamination of Arylboronic Acids and Esters: Reductive C–N Coupling with Nitromethane as a Methylamine Surrogate

Li, Gen; Qin, Ziyang; Radosevich, Alexander T.

doi:10.1021/jacs.0c08035

Cited by 55 publications

(26 citation statements)

References 88 publications

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“…Nitroalkane such as nitromethane or nitropropane has been adopted as substrate to couple with phenylboronic acid in the catalytic conditions, but no desired product was observed, judging from 1 H NMR and TLC analysis. The results are consistent with previously reported that the nitroalkane is inherently less reactive than Ar−NO 2 , due to a larger local frontier orbital energy gap (ΔΔ E =1.0 eV) [40] …”

Section: Resultssupporting

confidence: 93%

Reductive C−N Coupling of Nitroarenes: Heterogenization of MoO₃ Catalyst by Confinement in Silica

et al. 2021

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The construction of C−N bonds with nitroaromatics and boronic acids using highly efficient and recyclable catalysts remains a challenge. In this study, nanoporous MoO3 confined in silica serves as an efficient heterogeneous catalyst for C−N cross‐coupling of nitroaromatics with aryl or alkyl boronic acids to deliver N‐arylamines and with desirable multiple reusability. Experimental results suggest that silica not only heterogenizes the Mo species in the confined mesoporous microenvironment but also significantly reduces the reaction induction period and regulates the chemical efficiency of the targeted product. The well‐shaped MoO3@m−SiO2 catalyst exhibits improved catalytic performance both in yield and turnover number, in contrast with homogeneous Mo catalysts, commercial Pd/C, or MoO3 nanoparticles. This approach offers a new avenue for the heterogeneous catalytic synthesis of valuable bioactive molecules.

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Section: Resultssupporting

confidence: 93%

Reductive C−N Coupling of Nitroarenes: Heterogenization of MoO₃ Catalyst by Confinement in Silica

et al. 2021

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“…In addition, reductive amination of amines using CO 2 also constitutes a green methodology to produce N ‐methyl amines [6] . Apart from these approaches, reagents such as (para)formaldehyde, [7] formic acid, [8] dimethyl carbonate, [8f,9] DMSO, [10] Me‐NO 2 , [11] dimethylamines, [12] Me 3 N‐BH 3 [13] and methoxy unit of lignin [14] have been successfully employed to achieve useful N ‐methylamines or N , N ‐dimethylanilines. Traditionally, industrial N ‐methylation reactions are mainly performed using toxic reagents like methyl halides, dimethyl sulfate, dimethyl phosphite and diazomethane [15] .…”

Section: Introductionmentioning

confidence: 99%

Simple RuCl₃‐catalyzed N‐Methylation of Amines and Transfer Hydrogenation of Nitroarenes using Methanol

et al. 2021

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Methanol is a potential hydrogen source and C1 synthon, which finds interesting applications in both chemical synthesis and energy technologies. The effective utilization of this simple alcohol in organic synthesis is of central importance and attracts scientific interest. Herein, we report a clean and cost‐competitive method with the use of methanol as both C1 synthon and H2 source for selective N‐methylation of amines by employing relatively cheap RuCl3.xH2O as a ligand‐free catalyst. This readily available catalyst tolerates various amines comprising electron‐deficient and electron‐donating groups and allows them to transform into corresponding N‐methylated products in moderate to excellent yields. In addition, few marketed pharmaceutical agents (e. g., venlafaxine and imipramine) were also successfully synthesized via late‐stage functionalization from readily available feedstock chemicals, highlighting synthetic value of this advanced N‐methylation reaction. Using this platform, we also attempted tandem reactions with selected nitroarenes to convert them into corresponding N‐methylated amines using MeOH under H2‐free conditions including transfer hydrogenation of nitroarenes‐to‐anilines and prepared drug molecules (e. g., benzocaine and butamben) as well as key pharmaceutical intermediates. We further enable one‐shot selective and green syntheses of 1‐methylbenzimidazole using ortho‐phenylenediamine (OPDA) and methanol as coupling partners.

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“…However, not only the metals but also the metalloids and nonmetals are enjoying increased interest. Notably, phosphorus compounds were recently shown to catalyze C-N coupling reactions [113] and undergo both oxidative additions and reductive eliminations in stoichiometric experiments demonstrating potential as catalysts [114]. Main challenges include the design of the coordination sphere of the main-group element to stabilize active catalysts.…”

Section: Box 1 An Overview Of Homogeneous Catalysismentioning

confidence: 99%

Navigating through the Maze of Homogeneous Catalyst Design with Machine Learning

Gomes

Pollice

Aspuru‐Guzik

2021

Trends in Chemistry

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Microkinetic models of homogeneous catalytic reactions are constructed using ab initio simulations to gain insight into mechanisms, rationalize catalyst performance, and inspire catalyst design.Using a data-driven approach, the classical linear free-energy relationships are extended to multiple linear regression to study both reactivity and selectivity of homogeneous catalysts and build models to rationalize important interactions.Volcano plots are demonstrated as a general analysis framework when comparing potential energy surfaces of related catalytic reactions to extract decisive parameters and visualize breaks in mechanisms.Nonlinear regression models including random forests, support-vector machines, Gaussian processes, and artificial neural networks are applied to predict reaction yields, enantioselectivity, and activation energies of catalytic reactions based on both experimental and computational data.

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P(III)/P(V)-Catalyzed Methylamination of Arylboronic Acids and Esters: Reductive C–N Coupling with Nitromethane as a Methylamine Surrogate

Cited by 55 publications

References 88 publications

Reductive C−N Coupling of Nitroarenes: Heterogenization of MoO₃ Catalyst by Confinement in Silica

Reductive C−N Coupling of Nitroarenes: Heterogenization of MoO₃ Catalyst by Confinement in Silica

Simple RuCl₃‐catalyzed N‐Methylation of Amines and Transfer Hydrogenation of Nitroarenes using Methanol

Navigating through the Maze of Homogeneous Catalyst Design with Machine Learning

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P(III)/P(V)-Catalyzed Methylamination of Arylboronic Acids and Esters: Reductive C–N Coupling with Nitromethane as a Methylamine Surrogate

Cited by 55 publications

References 88 publications

Reductive C−N Coupling of Nitroarenes: Heterogenization of MoO3 Catalyst by Confinement in Silica

Reductive C−N Coupling of Nitroarenes: Heterogenization of MoO3 Catalyst by Confinement in Silica

Simple RuCl3‐catalyzed N‐Methylation of Amines and Transfer Hydrogenation of Nitroarenes using Methanol

Navigating through the Maze of Homogeneous Catalyst Design with Machine Learning

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Product

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Reductive C−N Coupling of Nitroarenes: Heterogenization of MoO₃ Catalyst by Confinement in Silica

Reductive C−N Coupling of Nitroarenes: Heterogenization of MoO₃ Catalyst by Confinement in Silica

Simple RuCl₃‐catalyzed N‐Methylation of Amines and Transfer Hydrogenation of Nitroarenes using Methanol