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Buchwald-Hartwig Amination of Aryl Halides with Heterocyclic Amines in the Synthesis of Highly Fluorescent Benzodifuran-Based Star-Shaped Organic Semiconductors.

ABSTRACT: The study of palladium-catalyzed amination of bromobenzene with aromatic and heterocyclic amines, widely used in the synthesis of organic semiconductors, was performed. The best conditions for the coupling of aryl bromides with carbazole, diphenylamine, phenoxazine, phenothiazine, 9,9-dimethyl-9,10-dihydroacridine, and their derivatives have been developed. Based on the results, nine new star-shaped organic semiconductors, exhibiting up to 100% fluorescent quantum yield in the 400-550 nm range, have been synthesized in good yields. The TDDFT calculations of the absorption spectra revealed a good correlation with experimental results and slight solvatochromic effects with a change in the polarity of the solvent.

SUBMITTER: Bosiak MJ

PROVIDER: S-EPMC8689646 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Rapidly Activating Pd-Precatalyst for Suzuki-Miyaura and Buchwald-Hartwig Couplings of Aryl Esters.

Project description:Esters are valuable electrophiles for cross-coupling due to their ubiquity and ease of synthesis. However, harsh conditions are traditionally required for the effective cross-coupling of ester substrates. Utilizing a recently discovered precatalyst, Pd-catalyzed Suzuki-Miyaura and Buchwald-Hartwig reactions involving cleavage of the C(acyl)-O bond of aryl esters that proceed under mild conditions are reported. The Pd(II) precatalyst is highly active because it is reduced to the Pd(0) active species more rapidly than previous precatalysts.

| S-EPMC5786428 | biostudies-literature

Rapid Evaluation of the Mechanism of Buchwald–Hartwig Amination and Aldol Reactions Using Intramolecular 13C Kinetic Isotope Effects

Project description:A practical approach is introduced for the rapid determination of 13C kinetic isotope effects that utilizes a “designed” reactant with two identical reaction sites. The mechanism of the Buchwald–Hartwig amination of tert-butylbromobenzene with primary and secondary amines is investigated under synthetically relevant catalytic conditions using traditional intermolecular 13C NMR methodology at natural abundance. Switching to 1,4-dibromobenzene, a symmetric bromoarene as the designed reactant, the same experimental 13C KIEs are determined using an intramolecular KIE approach. This rapid methodology for KIE determination requires substantially less material and time compared to traditional approaches. Details of the Buchwald–Hartwig amination mechanism are investigated under varying synthetic conditions, namely a variety of halides and bases. The enantioselectivity-determining step of the l-proline catalyzed aldol reaction is also evaluated using this approach. We expect this mechanistic methodology to gain traction among synthetic chemists as a practical technique to rapidly obtain high-resolution information regarding the transition structure of synthetically relevant reactions under catalytic conditions. Graphical Abstract

| S-EPMC8516138 | biostudies-literature

A new nanomagnetic Pd-Co bimetallic alloy as catalyst in the Mizoroki-Heck and Buchwald-Hartwig amination reactions in aqueous media.

Project description:A Pd-Co bimetallic alloy encapsulated in melamine-based dendrimer supported on magnetic nanoparticles denoted as γ-Fe2O3@MBD/Pd-Co was synthesized by a facile co-complexation-reduction method and characterized sufficiently. The catalytic evaluation of γ-Fe2O3@MBD/Pd-Co showed promising results in the Mizoroki-Heck and Buchwald-Hartwig amination reactions of various iodo-, bromo- and challenging chloroarenes in aqueous media. The synergetic cooperative effect of both Pd and Co and dispersion of the catalyst in water due to the encapsulation of γ-Fe2O3 by melamine-based dendrimer lead to high catalytic performance compared with the monometallic counterparts. The dispersion of the magnetic catalyst also facilitates the recovery and reuse of the catalyst by ten consecutive extraction and final magnetic isolation with no loss of catalytic activity, keeping its structure unaltered.

| S-EPMC8382703 | biostudies-literature

Lithium sensors based on photophysical changes of 1-aza-12-crown-4 naphthalene derivatives synthesized <i>via</i> Buchwald-Hartwig amination.

Project description:Lithium detection is of great significance in many applications. Lithium-sensing compounds with high selectivity are scarce and, if any, complicated to synthesize. We herein report a novel yet simple compound that can detect lithium ions in an organic solvent through changes in absorbance and fluorescence. Naphthalene functionalized with 1-aza-12-crown-4 (1) was synthesized via one step from commercially available 1-bromonaphthalene through Buchwald-Hartwig amination. In order to obtain a structure-property relationship, we also synthesized two other compounds that are structurally similar to 1, wherein the compounds 2 and 3 include an imide moiety (an electron acceptor) and do not include a 1-aza-12-crown-4 unit, respectively. Upon the addition of lithium ions, compound 1 displayed a clear isosbestic point in the absorption spectra and a new peak in the fluorescence spectra, whereas the compounds 2 and 3 indicated miniscule and no spectroscopic changes, respectively. 1H NMR titration studies and the calculated optimized geometry from density functional theory (DFT) indicated the lithium binding on the aza-crown. The calculated limit of detection (LOD) was 21 μM. The lithium detection with 1 is selective among other alkali metals (Na+, K+, and Cs+). DFT calculation indicated that the lone pair electrons in the nitrogen atom of 1 is delocalized yet available to bind lithium, whereas the nitrogen lone pair electrons of 2 showed significant intramolecular charge transfer to the imide acceptor, resulting in a high dipole moment, and thus were unavailable to bind lithium. This work elucidates the key design parameters for future lithium sensors.

| S-EPMC9641676 | biostudies-literature

Pd-Catalyzed Amination of Base-Sensitive Five-Membered Heteroaryl Halides with Aliphatic Amines.

Project description:We report a versatile and functional-group-tolerant method for the Pd-catalyzed C-N cross-coupling of five-membered heteroaryl halides with primary and secondary amines, an important but underexplored transformation. Coupling reactions of challenging, pharmaceutically relevant heteroarenes, such as 2-H-1,3-azoles, are reported in good-to-excellent yields. High-yielding coupling reactions of a wide set of five-membered heteroaryl halides with sterically demanding α-branched cyclic amines and acyclic secondary amines are reported for the first time. The key to the broad applicability of this method is the synergistic combination of (1) the moderate-strength base NaOTMS, which limits base-mediated decomposition of sensitive five-membered heteroarenes that ultimately leads to catalyst deactivation, and (2) the use of a GPhos-supported Pd catalyst, which effectively resists heteroarene-induced catalyst deactivation while promoting efficient coupling, even for challenging and sterically demanding amines. Cross-coupling reactions between a wide variety of five-membered heteroaryl halides and amines are demonstrated, including eight examples involving densely functionalized medicinal chemistry building blocks.

| S-EPMC9988406 | biostudies-literature

GPhos Ligand Enables Production of Chiral N-Arylamines in a Telescoped Transaminase-Buchwald-Hartwig Amination Cascade in the Presence of Excess Amine Donor.

Project description:The combination of biocatalysis and chemocatalysis can be more powerful than either technique alone. However, combining the two is challenging due to typically very different reaction conditions. Herein, chiral N-aryl amines, key features of many active pharmaceutical ingredients, are accessed in excellent enantioselectivity (typically>99.5 % ee) by combining transaminases with the Buchwald-Hartwig amination. By employing a bi-phasic buffer-toluene system as well as the ligand GPhos, the telescoped cascade proceeded with up to 89 % overall conversion in the presence of excess alanine. No coupling to alanine was observed.

| S-EPMC9292530 | biostudies-literature

C-H functionalization of amines with aryl halides by nickel-photoredox catalysis.

Project description:We describe the functionalization of α-amino C-H bonds with aryl halides using a combination of nickel and photoredox catalysis. This direct C-H, C-X coupling uses inexpensive and readily available starting materials to generate benzylic amines, an important class of bioactive molecules. Mechanistically, this method features the direct arylation of α-amino radicals mediated by a nickel catalyst. This reactivity is demonstrated for a range of aryl halides and N-aryl amines, with orthogonal scope to existing C-H activation and photoredox methodologies. We also report reactions with several complex aryl halides, demonstrating the potential utility of this approach in late-stage functionalization.

| S-EPMC5207500 | biostudies-literature

What can reaction databases teach us about Buchwald-Hartwig cross-couplings?

Project description:Despite the widespread and increasing usage of Pd-catalyzed C-N cross couplings, finding good conditions for these reactions can be challenging. Practitioners mostly rely on few methodology studies or anecdotal experience. This is surprising, since the advent of data-driven experimentation and the large amount of knowledge in databases allow for data-driven insight. In this work, we address this by analyzing more than 62 000 Buchwald-Hartwig couplings gathered from CAS, Reaxys and the USPTO. Our meta-analysis of the reaction performance generates data-driven cheatsheets for reaction condition recommendation. It also provides an interactive tool to find rarer ligands with optimal performance regarding user-selected substrate properties. With this we give practitioners promising starting points. Furthermore, we study bias and diversity in the literature and summarize the current state of the reaction data, including its pitfalls. Hence, this work will also be useful for future data-driven developments such as the optimization of reaction conditions via machine learning.

| S-EPMC8378852 | biostudies-literature

Direct Aryl C-H Amination with Primary Amines Using Organic Photoredox Catalysis.

Project description:The direct catalytic C-H amination of arenes is a powerful synthetic strategy with useful applications in pharmaceuticals, agrochemicals, and materials chemistry. Despite the advances in catalytic C-H functionalization, the use of aliphatic amine coupling partners is limited. Described herein is the construction of C-N bonds, using primary amines, by direct C-H functionalization with an acridinium photoredox catalyst under an aerobic atmosphere. A wide variety of primary amines, including amino acids and more complex amines are competent coupling partners. Various electron-rich aromatics and heteroaromatics are useful scaffolds in this reaction, as are complex, biologically active arenes. We also describe the ability to functionalize arenes that are not oxidized by an acridinium catalyst, such as benzene and toluene, thus supporting a reactive amine cation radical intermediate.

| S-EPMC5995118 | biostudies-literature

Concatenating Suzuki Arylation and Buchwald-Hartwig Amination by A Sequentially Pd-Catalyzed One-Pot Process-Consecutive Three-Component Synthesis of C,N-Diarylated Heterocycles.

Project description:The concatenation of Suzuki coupling and Buchwald-Hartwig amination in a consecutive multicomponent reaction opens a concise, modular and efficient one-pot approach to diversely functionalized heterocycles, as exemplified for 3,10-diaryl 10H-phenothiazines, 3,9-diaryl 9H-carbazoles, and 1,5-diaryl 1H-indoles, in high yields starting from simple staring materials. Moreover, this one-pot reaction is a sequentially palladium-catalyzed process that does not require additional catalyst loading after the first coupling step.

| S-EPMC7756286 | biostudies-literature

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