Browse
Submit Data
Databases
API
Help

Dataset Information

69 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Visible-Light-Driven Stereoselective Annulation of Alkyl Anilines and Dibenzoylethylenes via Electron Donor-Acceptor Complexes.

ABSTRACT: A catalyst-free, stereoselective visible-light-driven annulation reaction between alkenes and N,N-substituted dialkyl anilines for the synthesis of substituted tetrahydroquinolines is presented. The reaction is driven by the photoexcitation of an electron donor-acceptor (EDA) complex, and the resulting products are obtained in good to high yields with complete diastereoselectivity. Mechanistic rationale and photochemical characterization of the EDA-complex are provided.

SUBMITTER: Runemark A

PROVIDER: S-EPMC7884011 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Visible-Light-Driven Stereoselective Annulation of Alkyl Anilines and Dibenzoylethylenes via Electron Donor-Acceptor Complexes.

Runemark August A Zacharias Savannah C SC Sundén Henrik H

The Journal of organic chemistry 20210104 2

A catalyst-free, stereoselective visible-light-driven annulation reaction between alkenes and N,N-substituted dialkyl anilines for the synthesis of substituted tetrahydroquinolines is presented. The reaction is driven by the photoexcitation of an electron donor-acceptor (EDA) complex, and the resulting products are obtained in good to high yields with complete diastereoselectivity. Mechanistic rationale and photochemical characterization of the EDA-complex are provided. ...[more]

PMID: 33397115

Similar Datasets

Overcoming Back Electron Transfer in the Electron Donor-Acceptor Complex-Mediated Visible Light-Driven Generation of α-Aminoalkyl Radicals from Secondary Anilines.

Project description:An additive-free, visible light-driven annulation between N-aryl amino acids and maleimide to form tetrahydroquinolines (THQs) is disclosed. Photochemical activation of an electron donor-acceptor (EDA) complex between amino acids and maleimides drives the reaction, and aerobic oxygen acts as the terminal oxidant in the net oxidative process. A range of N-aryl amino acids and maleimides have been investigated as substrates to furnish the target THQ in good to excellent yield. Mechanistic investigations, including titration and UV-vis studies, demonstrate the key role of the EDA complex as the photoactive species.

| S-EPMC9830629 | biostudies-literature

(4+3) Annulation of Donor-Acceptor Cyclopropanes and Azadienes: Highly Stereoselective Synthesis of Azepanones.

Project description:Azepanes are important seven-membered heterocycles, which are present in numerous natural and synthetic compounds. However, the development of convergent synthetic methods to access them remains challenging. Herein, we report the Lewis acid catalyzed (4+3) annulative addition of aryl and amino donor-acceptor cyclopropanes with 2-aza-1,3-dienes. Densely substituted azepane derivatives were obtained in good to excellent yields and with high diastereoselectivity. The reaction occurred under mild conditions with ytterbium triflate as the catalyst. The use of copper triflate with a trisoxazoline (Tox) ligand led to an enantioselective transformation. The obtained cycloadducts were convenient substrates for a series of further modifications, showing the synthetic utility of these compounds.

| S-EPMC9545371 | biostudies-literature

Visible-Light-Driven C-S Bond Formation Based on Electron Donor-Acceptor Excitation and Hydrogen Atom Transfer Combined System.

Project description:Developed herein is a visible-light-driven synthesis of sulfides by an electron donor-acceptor/single electron transfer and hydrogen atom transfer combined system without transition metals and strong oxidants. This reaction proceeds through the excitation of an electron donor-acceptor complex between a thiolate and an aryl halide, followed by the hydrogen atom transfer from an alkane to the generated aryl radical.

| S-EPMC9954416 | biostudies-literature

Triarylamines as catalytic donors in light-mediated electron donor-acceptor complexes.

Project description:Recently, photochemistry of Electron Donor-Acceptor (EDA) complexes employing catalytic amounts of electron donors have become of interest as a new methodology in the catalysis field, allowing for decoupling of the electron transfer (ET) from the bond-forming event. However, examples of practical EDA systems in the catalytic regime remain scarce, and their mechanism is not yet well-understood. Herein, we report the discovery of an EDA complex between triarylamines and α-perfluorosulfonylpropiophenone reagents, catalyzing C-H perfluoroalkylation of arenes and heteroarenes under visible light irradiation in pH- and redox-neutral conditions. We elucidate the mechanism of this reaction using a detailed photophysical characterization of the EDA complex, the resulting triarylamine radical cation, and its turnover event.

| S-EPMC10055340 | biostudies-literature

Selective Coupling of 1,2-Bis-Boronic Esters at the more Substituted Site through Visible-Light Activation of Electron Donor-Acceptor Complexes.

Project description:1,2-Bis-boronic esters are useful synthetic intermediates particularly as the two boronic esters can be selectively functionalized. Usually, the less hindered primary boronic ester reacts, but herein, we report a coupling reaction that enables the reversal of this selectivity. This is achieved through the formation of a boronate complex with an electron-rich aryllithium which, in the presence of an electron-deficient aryl nitrile, leads to the formation of an electron donor-acceptor complex. Following visible-light photoinduced electron transfer, a primary radical is generated which isomerizes to the more stable secondary radical before radical-radical coupling with the arene radical-anion, giving β-aryl primary boronic ester products. The reactions proceed under catalyst-free conditions. This method also allows stereodivergent coupling of cyclic cis-1,2-bis-boronic esters to provide trans-substituted products, complementing the selectivity observed in the Suzuki-Miyaura reaction.

| S-EPMC9314813 | biostudies-literature

Donor-Acceptor Pyridinium Salts for Photo-Induced Electron-Transfer-Driven Modification of Tryptophan in Peptides, Proteins, and Proteomes Using Visible Light.

Project description:Tryptophan (Trp) plays a variety of critical functional roles in protein biochemistry; however, owing to its low natural frequency and poor nucleophilicity, the design of effective methods for both single protein bioconjugation at Trp as well as for in situ chemoproteomic profiling remains a challenge. Here, we report a method for covalent Trp modification that is suitable for both scenarios by invoking photo-induced electron transfer (PET) as a means of driving efficient reactivity. We have engineered biaryl N-carbamoyl pyridinium salts that possess a donor-acceptor relationship that enables optical triggering with visible light whilst simultaneously attenuating the probe's photo-oxidation potential in order to prevent photodegradation. This probe was assayed against a small bank of eight peptides and proteins, where it was found that micromolar concentrations of the probe and short irradiation times (10-60 min) with violet light enabled efficient reactivity toward surface exposed Trp residues. The carbamate transferring group can be used to transfer useful functional groups to proteins including affinity tags and click handles. DFT calculations and other mechanistic analyses reveal correlations between excited state lifetimes, relative fluorescence quantum yields, and chemical reactivity. Biotinylated and azide-functionalized pyridinium salts were used for Trp profiling in HEK293T lysates and in situ in HEK293T cells using 440 nm LED irradiation. Peptide-level enrichment from live cell labeling experiments identified 290 Trp modifications, with 82% selectivity for Trp modification over other π-amino acids, demonstrating the ability of this method to identify and quantify reactive Trp residues from live cells.

| S-EPMC10124759 | biostudies-literature

Photoinduced Electron Transfer in Donor-Acceptor Complexes: Isotope Effect and Dynamic Symmetry Breaking.

Project description:Electron-nuclear (vibronic) coupling has emerged as an important factor in determining the efficiency of energy transfer and charge separation in natural and artificial photosynthetic systems. Here we investigate the photoinduced charge-transfer process in a hydrogen-bonded donor-acceptor molecular complex. By using real-time quantum-classical simulations based on time-dependent Kohn-Sham equations, we follow in detail the relaxation from the Franck-Condon point to the region of strong nonadiabatic coupling where electron transfer occurs. We elucidate how the charge transfer is coupled to specific vibrational modes and how it is affected by isotope substitution. The importance of resonance in nuclear and electron dynamics and the role of dynamic symmetry breaking are emphasized. Using the dipole moment as a descriptive parameter, exchange of angular momentum between nuclear and electronic subsystems in an electron-nuclear resonant process is inferred. The performed simulations support a nonadiabatic conversion via adiabatic passage process that was recently put forward. These results are relevant in deriving rational design principles for solar-to-fuel conversion devices.

| S-EPMC6844126 | biostudies-literature

Tunable Donor-Acceptor Linear Conjugated Polymers Involving Cyanostyrylthiophene Linkages for Visible-Light-Driven Hydrogen Production.

Project description:In this paper, an atom- and step-economic direct C-H arylation polymerization (DArP) strategy was developed to access cyanostyrylthiophene (CST)-based donor-acceptor (D-A) conjugated polymers (CPs) used for photocatalytic hydrogen production (PHP) from water reduction. The new CST-based CPs CP1-CP5 with varied building blocks were systematically studied by X-ray single-crystal analysis, FTIR, scanning electron microscopy, UV-vis, photoluminescence, transient photocurrent response, cyclic voltammetry measurements, and a PHP test, which showed that the phenyl-cyanostyrylthiophene-based CP3 exhibits a superior hydrogen evolution rate (7.60 mmol h-1 g-1) compared to other conjugated polymers. The structure-property-performance correlation results obtained in this study will provide an important guideline for the rational design of high-performance D-A CPs for PHP applications.

| S-EPMC10004844 | biostudies-literature

Catalytic (3 + 2) annulation of donor-acceptor aminocyclopropane monoesters and indoles.

Project description:The efficient catalytic activation of donor-acceptor aminocyclopropanes lacking the commonly used diester acceptor is reported here in a (3 + 2) dearomative annulation with indoles. Bench-stable tosyl-protected aminocyclopropyl esters were converted into cycloadducts in 46-95% yields and up to 95 : 5 diastereomeric ratio using catalytic amounts of triethylsilyl triflimide. Tricyclic indoline frameworks containing four stereogenic centers including all-carbon quaternary centers were obtained.

| S-EPMC8246098 | biostudies-literature

Photochemical C(sp2 )-H Pyridination via Arene-Pyridinium Electron Donor-Acceptor Complexes.

Project description:This report describes the development of a photochemical method for C(sp2 )-H pyridination that leverages the photoexcitation of electron donor-acceptor (EDA) complexes. Experimental and DFT studies show that black light (λmax ≈350 nm) irradiation of solutions of protonated pyridines (acceptors) and aromatic C-H substrates (donors) results in single electron transfer to form aryl radical cation intermediates that can be trapped with pyridine nucleophiles under aerobic conditions. With some modification of the reaction conditions, this EDA activation mode is also effective for promoting the oxidatively triggered SN Ar pyridination of aryl halides. Overall, this report represents an inexpensive and atom-economical approach to photochemical pyridination reactions that eliminates the requirement of an exogenous photocatalyst.

| S-EPMC9828204 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data