Iron‐Catalyzed Chemoselective C−N Coupling Reaction: A Protecting‐Group‐Free Amination of Aryl Halides Bearing Amino or Hydroxy Groups

Aoki, Yuji; Toyoda, Takahiro; Kawasaki, H.; Takaya, Hikaru; Sharma, Akhilesh K.; Morokuma, Keiji; Nakamura, Masaharu

doi:10.1002/ajoc.201900641

Cited by 10 publications

(5 citation statements)

References 55 publications

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“…To address this, it was necessary to expand the ADs of the yield prediction models and design new experimental conditions. Therefore, after the two samples in Table were added to the initial 73 samples, we collected experimental datasets described in scientific papers on BHCC and SMCC reactions − and added them to our dataset to increase the scope of the catalyst structures and experimental conditions. The added experimental datasets included catalysts with transition metals such as Ni, Pd, Cu, Fe, and so forth and ligands that are different from our dataset.…”

Section: Resultsmentioning

confidence: 99%

“…Since we focused on the combination of catalysts and ligands, we used the same experimental conditions for the solvent, base, reaction time, and reaction temperature as in our dataset. For the experimental catalysts and ligands, 33 catalysts from our dataset and 23 from collected papers − were employed, and 52,000 compounds from the Namiki Shoji database were used as ligands.…”

Section: Resultsmentioning

confidence: 99%

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Design of Experimental Conditions with Machine Learning for Collaborative Organic Synthesis Reactions Using Transition-Metal Catalysts

et al. 2021

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To improve product yields in synthetic reactions, it is important to use appropriate catalysts. In this study, we used machine learning to design catalysts for a reaction system in which both Buchwald−Hartwig-type and Suzuki−Miyaura-type cross-coupling reactions proceed simultaneously. First, using an existing dataset, yield prediction models were constructed with machine learning between experimental conditions, including the substrate and catalyst and the yields of the two products. Seven methods for calculating both the substrate and catalyst descriptors were proposed, and the predictive ability of the yield prediction models was discussed in terms of the descriptors and machine learning methods. Then, the constructed models were used to predict the compound yields for new combinations of substrates and catalysts, and the predictions were experimentally validated with high reproducibility, confirming that machine learning can predict yields from experimental conditions with high accuracy. In addition, to design catalysts that will improve the yields in our dataset, we added datasets collected from scientific papers and designed catalyst ligands. The proposed catalyst candidates were tested in actual synthetic experiments, and the experimental results exceeded the existing yields.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Design of Experimental Conditions with Machine Learning for Collaborative Organic Synthesis Reactions Using Transition-Metal Catalysts

et al. 2021

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“…Recently, the same group [24] reported another iron-catalyzed chemoselective CÀ N coupling reaction of diarylamines with aryl halides bearing a free amino group (Scheme 6). Preliminary DFT studies indicated that the reaction involved a dimeric-Fe active species, and the chemoselectivity was controlled by kinetics.…”

Section: Iron-catalyzed Csp 2 -N Bond Formationmentioning

confidence: 99%

Iron‐Catalyzed Cross‐Coupling Reactions for the Construction of Carbon‐Heteroatom Bonds

et al. 2020

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Carbon-heteroatom bonds are ubiquitous among pesticides, pharmaceutical agents, and natural products. In recent years, significant progress has been made in transition-metal-catalyzed carbon-heteroatom bond formation. Especially, iron-catalyzed reactions have become a focused area in organic chemistry owing to their advantages of low cost, economical and environmental benignity. This review intends to summarize the recent advances in the construction of carbon-heteroatom bonds via cross-coupling reactions using iron as a catalyst, including the formation of CÀ N, CÀ O, CÀ S, CÀ B, and CÀ Si bonds. A series of nucleophilic heteroatoms reagents, reaction classifications, and iron catalytic systems are discussed. In addition, some mechanistic studies have also been described. formation of CÀ N, CÀ O, CÀ S, CÀ B, and CÀ Si bonds are mainly focused. 2. Iron-Catalyzed CÀ N Bond Formation The construction of CÀ N bond by transition metal-catalyzed is one of the most significant transformations in organic synthesis, which is widely employed in chemical, pharmaceutical, and materials industries. [8] The classical method to access CÀ N bond is through the transition metal-catalyzed cross-coupling reaction between aryl or alkenyl halides and amines, also known as Buchwald-Hartwig amination reaction. In recent years, the formation of CÀ N bond via CÀ H activation has been welldocumented. [9] After decades of development, the great progress has been achieved in the transition metals (Cu, Pd, Ni, Fe, Co) catalyzed the construction of the CÀ N bond. [10] However, compared with other transition metals, iron-catalyzed CÀ N bond formation has less been studied, which might be caused by the negative effect of trace metals. [21-22] 2.1. Iron-Catalyzed CspÀ N Bond Formation Alkynamines are essential compounds, widely used in organic reactions such as pericyclic reaction, tandem RCM, Pauson-Khand reaction, Kinugasa reaction, Saucy-Marbet rearrangement, and Ficini-Claisen rearrangement. [11] In 2009, Zhang and coworkers [11e] developed the first example of iron-catalyzed amination of alkynyl bromides (Scheme 1). Nucleophiles such as amide, sulfonamide, and indole could react with alkynyl bromides to obtain alkynamines in high yields under FeCl 3 * 6H 2 O and DMEDA catalytic system. This reaction exhibits good functional group tolerance, and the functional groups

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“…The C–N cross‐couplings executed by transition‐metal catalysts immersed eloquent part in the construction of a variety of commercially potent organic molecules. [ 28–30 ] Among the C–N coupled products, N ‐arylimidazoles and N ‐arylbenzimidazoles draw considerable attention due to their widespread use in organocatalysis, ionic liquids, and pharmaceutical, biological, and material interest. [ 29,31–33 ] Common strategies to access the arylated amines include (i) the activation of aryl halide/ethers/esters toward aromatic nucleophilic substitution (S N Ar) using amines, [ 34–36 ] (ii) Ullmann/Buchwald–Hartwig coupling of aryl halides and amines, [ 37–40 ] and (iii) Chan–Lam coupling of arylamines and arylboronic acids.…”

Section: Introductionmentioning

confidence: 99%

Cu(OAc)₂‐porphyrins as an efficient catalytic system for base‐free, nature mimicking Chan–Lam coupling in water

Venkateswarlu

Rao

2021

Applied Organom Chemis

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The use of porphyrins as ligands in organic synthesis reveals the natural process, because these are the constituent motifs of catalysts in many bio‐organic reactions. This article presents the synthesis of two N‐pincer tetradentate porphyrins; tetrasodium meso‐tetra(p‐sulfonatophenyl)phorphyrin (H2TSTpSPP) and meso‐tetra(m‐carboxyphenyl)porphyrin (H2TmCPP), and study on their aptness for Cu‐catalyzed C–N coupling reactions of arylboronic acids and amines (Chan–Lam coupling reaction) in water under external base free conditions. The porphyrins and Chan–Lam coupling products were well characterized by their spectral analysis. The high product yields, application of nature‐inspired conditions, large extent of substrates, ease of making and handling the ligands, avoidance of base, and use of water as reaction media are the attractive attributes of this finding.

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Iron‐Catalyzed Chemoselective C−N Coupling Reaction: A Protecting‐Group‐Free Amination of Aryl Halides Bearing Amino or Hydroxy Groups

Cited by 10 publications

References 55 publications

Design of Experimental Conditions with Machine Learning for Collaborative Organic Synthesis Reactions Using Transition-Metal Catalysts

Design of Experimental Conditions with Machine Learning for Collaborative Organic Synthesis Reactions Using Transition-Metal Catalysts

Iron‐Catalyzed Cross‐Coupling Reactions for the Construction of Carbon‐Heteroatom Bonds

Cu(OAc)₂‐porphyrins as an efficient catalytic system for base‐free, nature mimicking Chan–Lam coupling in water

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Iron‐Catalyzed Chemoselective C−N Coupling Reaction: A Protecting‐Group‐Free Amination of Aryl Halides Bearing Amino or Hydroxy Groups

Cited by 10 publications

References 55 publications

Design of Experimental Conditions with Machine Learning for Collaborative Organic Synthesis Reactions Using Transition-Metal Catalysts

Design of Experimental Conditions with Machine Learning for Collaborative Organic Synthesis Reactions Using Transition-Metal Catalysts

Iron‐Catalyzed Cross‐Coupling Reactions for the Construction of Carbon‐Heteroatom Bonds

Cu(OAc)2‐porphyrins as an efficient catalytic system for base‐free, nature mimicking Chan–Lam coupling in water

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Cu(OAc)₂‐porphyrins as an efficient catalytic system for base‐free, nature mimicking Chan–Lam coupling in water