Browse
Submit Data
Databases
API
Help

Dataset Information

31 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

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

ABSTRACT: 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.

SUBMITTER: Wang H

PROVIDER: S-EPMC9314813 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Copper-Catalyzed Coupling of Thioamides and Donor/Acceptor-Substituted Carbenoids: Synthesis of Enamino Esters and Enaminones.

Project description:The coupling of thioamides and donor/acceptor-substituted diazocarbonyl compounds is reported for the first time. The present report provides a mild, catalytic method that couples thioamides and donor/acceptor-substituted diazocarbonyl compounds to form enamino esters and enaminones. Unlike traditional methods for the synthesis of enamino esters and enaminones from thioamides, both N-alkyl thioamides and thiocarbamates are suitable substrates in this coupling reaction. Copper(I) bromide catalyzes the reaction and provides enamino esters and enaminones chemo- and diastereoselectively in less time than Rh2(OAc)4 or Ru(PPh3)3Cl2 catalysts.

| S-EPMC6648369 | biostudies-literature

Visible-Light-Mediated Decarboxylative Radical Additions to Vinyl Boronic Esters: Rapid Access to γ-Amino Boronic Esters.

Project description:The synthesis of alkyl boronic esters by direct decarboxylative radical addition of carboxylic acids to vinyl boronic esters is described. The reaction proceeds under mild photoredox catalysis and involves an unprecedented single-electron reduction of an α-boryl radical intermediate to the corresponding anion. The reaction is amenable to a diverse range of substrates, including α-amino, α-oxy, and alkyl carboxylic acids, thus providing a novel method to rapidly access boron-containing molecules of potential biological importance.

| S-EPMC5838549 | biostudies-literature

Enantiospecific Synthesis of ortho-Substituted Benzylic Boronic Esters by a 1,2-Metalate Rearrangement/1,3-Borotropic Shift Sequence.

Project description:Coupling reactions between benzylamines and boronic esters have been investigated. ortho-Lithiated benzylamines react with boronic esters and a N-activator to afford ortho-substituted benzylic boronic esters with formal 1,1'-benzylidene insertion into the C-B bond. The reaction occurs by a SN2' elimination and 1,2-metalate rearrangement of the N-activated boronate complex to afford a dearomatized intermediate, which undergoes a Lewis-acid catalyzed 1,3-borotropic shift to afford the boronic ester products in high yield and with excellent enantiospecificity. The use of enantioenriched α-substituted benzylamines gave the corresponding secondary boronic esters with high ee.

| S-EPMC5520102 | biostudies-literature

Spectral fine tuning of cyanine dyes: electron donor-acceptor substituted analogues of thiazole orange.

Project description:The introduction of electron donor and acceptor groups at strategic locations on a fluorogenic cyanine dye allows fine-tuning of the absorption and emission spectra while preserving the ability of the dye to bind to biomolecular hosts such as double-stranded DNA and a single-chain antibody fragment originally selected for binding to the parent unsubstituted dye, thiazole orange (TO). The observed spectral shifts are consistent with calculated HOMO-LUMO energy gaps and reflect electron density localization on the quinoline half of TO in the LUMO. A dye bearing donating methoxy and withdrawing trifluoromethyl groups on the benzothiazole and quinoline rings, respectively, shifts the absorption spectrum to sufficiently longer wavelengths to allow excitation at green wavelengths as opposed to the parent dye, which is optimally excited in the blue.

| S-EPMC4557812 | biostudies-literature

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

Project description: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.

| S-EPMC7884011 | biostudies-literature

Acetoxy-Substituted Cyclopropane Dicarbonyls as Stable Donor-Acceptor-Acceptor Cyclopropanes.

Project description:A study of cyclopropanations of oxy-substituted ethenes with ethyl α-diazoaroyl acetates is described. Whereas trimethylsilyl vinyl ether and ethyl vinyl ether gave dihydrofuran products, stable cyclopropanes were isolated when vinyl acetate was used. Yields ranged from 0-87%, depending on the nature and position of the aryl ring substituent.

| S-EPMC4852370 | biostudies-literature

Long-range coupling of electron-hole pairs in spatially separated organic donor-acceptor layers.

Project description:Understanding exciton behavior in organic semiconductor molecules is crucial for the development of organic semiconductor-based excitonic devices such as organic light-emitting diodes and organic solar cells, and the tightly bound electron-hole pair forming an exciton is normally assumed to be localized on an organic semiconducting molecule. We report the observation of long-range coupling of electron-hole pairs in spatially separated electron-donating and electron-accepting molecules across a 10-nanometers-thick spacer layer. We found that the exciton energy can be tuned over 100 megaelectron volts and the fraction of delayed fluorescence can be increased by adjusting the spacer-layer thickness. Furthermore, increasing the spacer-layer thickness produced an organic light-emitting diode with an electroluminescence efficiency nearly eight times higher than that of a device without a spacer layer. Our results demonstrate the first example of a long-range coupled charge-transfer state between electron-donating and electron-accepting molecules in a working device.

| S-EPMC4771443 | biostudies-literature

Enantioselective Construction of Tertiary Boronic Esters by Conjunctive Cross-Coupling.

Project description:Catalytic enantioselective conjunctive cross-coupling has been developed to construct tertiary alkylboronic esters. These reactions occur with good yield and enantioselectivity for a range of substrates. Mechanistic experiments reveal aspects of the catalytic cycle that allow hindered substrates to react without significant complicating side reactions.

| S-EPMC6414220 | biostudies-literature

Phosphonate-Directed Catalytic Asymmetric Hydroboration: Delivery of Boron to the More Substituted Carbon, Leading to Chiral Tertiary Benzylic Boronic Esters.

Project description:Phosphonate-directed catalytic asymmetric hydroboration (CAHB) of β-aryl/heteroaryl methylidenes and trisubstituted alkenes by pinacolborane enables facile access to functionalized, chiral tertiary benzylic boronic esters. Hydroboration is catalyzed by a chiral rhodium catalyst prepared in situ from a Rh(I)-precursor in combination with a simple TADDOL-derived chiral cyclic monophosphite in a 1:1 ratio. The regio- and stereochemistry arises from the combined effects of the relative disposition of the directing group to the alkene, the alkene substitution pattern, and the necessity of an aryl substituent attached to the alkene. A range of aryl and heteroaryl substituents can be accommodated, and for several chiral substrates, the reactions are efficiently catalyst-controlled enabling the choice of diastereomeric products as desired. Stereospecific transformations of the chiral boronic ester afford chiral phosphonates bearing a quaternary carbon stereocenter. The synthetic utility of the products is further demonstrated by α-oxidation of the phosphonate leading to hydroxy- and oxo-phosphonates; the latter readily undergo elimination/substitution reactions to unmask the phosphonate functionality with the formation of aldehydes, alcohols, esters, amides, acids and ketones.

| S-EPMC6533611 | biostudies-literature

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

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