Browse
Submit Data
Databases
API
Help

Dataset Information

14 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Direct, stereoselective thioglycosylation enabled by an organophotoredox radical strategy.

ABSTRACT: While strategies involving a 2e^- transfer pathway have dictated glycosylation development, the direct glycosylation of readily accessible glycosyl donors as radical precursors is particularly appealing because of high radical anomeric selectivity and atom- and step-economy. However, the development of the radical process has been challenging owing to notorious competing reduction, elimination and/or S_N side reactions of commonly used, labile glycosyl donors. Here we introduce an organophotocatalytic strategy through which glycosyl bromides can be efficiently converted into corresponding anomeric radicals by photoredox mediated HAT catalysis without a transition metal or a directing group and achieve highly anomeric selectivity. The power of this platform has been demonstrated by the mild reaction conditions enabling the synthesis of challenging α-1,2-cis-thioglycosides, the tolerance of various functional groups and the broad substrate scope for both common pentoses and hexoses. Furthermore, this general approach is compatible with both sp² and sp³ sulfur electrophiles and late-stage glycodiversification for a total of 50 substrates probed.

SUBMITTER: Ji P

PROVIDER: S-EPMC8163235 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Enzyme-controlled stereoselective radical cyclization to arenes enabled by metalloredox biocatalysis.

Project description:The effective induction of high levels of stereocontrol for free radical-mediated transformations represents a notorious challenge in asymmetric catalysis. Herein, we describe a novel metalloredox biocatalysis strategy to repurpose natural cytochromes P450 to catalyse asymmetric radical cyclisation to arenes through an unnatural electron transfer mechanism. Empowered by directed evolution, engineered P450s allowed diverse radical cyclisation selectivities to be accomplished in a catalyst-controlled fashion: P450arc1 and P450arc2 facilitated enantioconvergent transformations of racemic substrates, giving rise to either enantiomer of the product with excellent total turnover numbers (up to 12,000). In addition to these enantioconvergent variants, another engineered radical cyclase, P450arc3, permitted efficient kinetic resolution of racemic chloride substrates (S factor = 18). Furthermore, computational studies revealed a proton-coupled electron transfer (PCET) mechanism for the radical-polar crossover step, suggesting the potential role of the haem carboxylate as a base catalyst. Collectively, the excellent tunability of this metalloenzyme family provides an exciting platform for harnessing free radical intermediates for asymmetric catalysis.

| S-EPMC10882986 | biostudies-literature

Organophotoredox-catalyzed semipinacol rearrangement via radical-polar crossover.

Project description:Over the past century, significant progress in semipinacol rearrangement involving 1,2-migration of α-hydroxy carbocations has been made in the areas of catalysis and total synthesis of natural products. To access the α-hydroxy carbocation intermediate, conventional acid-mediated or electrochemical approaches have been employed. However, the photochemical semipinacol rearrangement has been underdeveloped. Herein, we report the organophotoredox-catalyzed semipinacol rearrangement via radical-polar crossover (RPC). A phenothiazine-based organophotoredox catalyst facilitates the generation of an α-hydroxy non-benzylic alkyl radical followed by oxidation to the corresponding carbocation, which can be exploited to undergo the semipinacol rearrangement. As a result, the photochemical approach enables decarboxylative semipinacol rearrangement of β-hydroxycarboxylic acid derivatives and alkylative semipinacol type rearrangement of allyl alcohols with carbon electrophiles, producing α-quaternary or α-tertiary carbonyls bearing sp3-rich scaffolds.

| S-EPMC9106707 | biostudies-literature

Room-temperature Pd/Ag direct arylation enabled by a radical pathway.

Project description:Direct arylation is an appealing method for preparing π-conjugated materials, avoiding the prefunctionalization required for traditional cross-coupling methods. A major effort in organic electronic materials development is improving the environmental and economic impact of production; direct arylation polymerization (DArP) is an effective method to achieve these goals. Room-temperature polymerization would further improve the cost and energy efficiencies required to prepare these materials. Reported herein is new mechanistic work studying the underlying mechanism of room temperature direct arylation between iodobenzene and indole. Results indicate that room-temperature, Pd/Ag-catalyzed direct arylation systems are radical-mediated. This is in contrast to the commonly proposed two-electron mechanisms for direct arylation and appears to extend to other substrates such as benzo[b]thiophene and pentafluorobenzene.

| S-EPMC7082708 | biostudies-literature

Regioselective Fluoroalkylarylation of Enamides Enabled by an Iron-Catalyzed Multicomponent Radical Cross-Coupling Strategy.

Project description:Fluoroalkylated compounds are important entities in agrochemicals, pharmaceuticals, and materials. The catalytic dicarbofunctionalization of alkenes represents a powerful strategy for the rapid construction and diversification of compounds. In this vein, multicomponent cross-coupling reactions (MC-CCR) can provide an efficient synthetic route to build molecular complexity. In this work, we report the first iron-catalyzed three-component fluoroalkylarylation of enamides via selective formation and trapping of α-amide radicals under mild conditions and fast reaction times. The reaction tolerates a variety of commercially available aryl Grignard reagents and fluoroalkyl halides. Finally, the use of a removable phthalimido group provides an efficient strategy to prepare highly valuable γ-difluoroalkylated amines.

| S-EPMC10863403 | biostudies-literature

Direct Access to α-Aminosilanes Enabled by Visible-Light-Mediated Multicomponent Radical Cross-Coupling.

Project description:α-Aminosilanes are an important class of organic compounds that show biological activity. In this communication, a new approach to α-aminosilanes that utilizes photoredox catalysis to enable three-component coupling of organo(tristrimethylsilyl)silanes with feedstock alkylamines and aldehydes is presented. A wide range of highly functionalized α-aminosilanes can be obtained in good yields under mild conditions. Both primary amines and secondary amines are compatible with this transformation. Moreover, optically pure α-aminosilanes are accessible by using chiral amines. Mechanistic studies indicate that reactions proceed through radical/radical cross-coupling of silyl radicals with α-amino alkyl radicals.

| S-EPMC8596805 | biostudies-literature

Synthesis and Suzuki-Miyaura Cross-Coupling of Alkyl Amine-Boranes. A Boryl Radical-Enabled Strategy.

Project description:Alkyl organoborons are powerful materials for the construction of C(sp3)-C(sp2) bonds, predominantly via Suzuki-Miyaura cross-coupling. These species are generally assembled using 2-electron processes that harness the ability of boron reagents to act as both electrophiles and nucleophiles. Herein, we demonstrate an alternative borylation strategy based on the reactivity of amine-ligated boryl radicals. This process features the use of a carboxylic acid containing amine-ligated borane that acts as boryl radical precursor for photoredox oxidation and decarboxylation. The resulting amine-ligated boryl radical undergoes facile addition to styrenes and imines through radical-polar crossover manifolds. This delivers a new class of sp3-organoborons that are stable solids and do not undergo protodeboronation. These novel materials include unprotected α-amino derivatives that are generally unstable. Crucially, these aliphatic organoboron species can be directly engaged in Suzuki-Miyaura cross-couplings with structurally complex aryl halides. Preliminary studies suggest that they enable slow-release of the corresponding and often difficult to handle alkyl boronic acids.

| S-EPMC11363021 | biostudies-literature

Direct transfer of tri- and di-fluoroethanol units enabled by radical activation of organosilicon reagents.

Project description:Trifluoroethanol and difluoroethanol units are important motifs in bioactive molecules, but the methods to direct incorporate these units are limited. Herein, we report two organosilicon reagents for the transfer of trifluoroethanol and difluoroethanol units into molecules. Through intramolecular C-Si bond activation by alkoxyl radicals, these reagents were applied in allylation, alkylation and alkenylation reactions, enabling efficient synthesis of various tri(di)fluoromethyl group substituted alcohols. The broad applicability and general utility of the approach are highlighted by late-stage introduction of these fluoroalkyl groups to complex molecules, and the synthesis of antitumor agent Z and its difluoromethyl analog Z'.

| S-EPMC7265496 | biostudies-literature

Photoexcitation of flavoenzymes enables a stereoselective radical cyclization.

Project description:Photoexcitation is a common strategy for initiating radical reactions in chemical synthesis. We found that photoexcitation of flavin-dependent "ene"-reductases changes their catalytic function, enabling these enzymes to promote an asymmetric radical cyclization. This reactivity enables the construction of five-, six-, seven-, and eight-membered lactams with stereochemical preference conferred by the enzyme active site. After formation of a prochiral radical, the enzyme guides the delivery of a hydrogen atom from flavin-a challenging feat for small-molecule chemical reagents. The initial electron transfer occurs through direct excitation of an electron donor-acceptor complex that forms between the substrate and the reduced flavin cofactor within the enzyme active site. Photoexcitation of promiscuous flavoenzymes has thus furnished a previously unknown biocatalytic reaction.

| S-EPMC7028431 | biostudies-literature

Stereoselective Directed Cationic Cascades Enabled by Molecular Anchoring in Terpene Cyclases.

Project description:Cascade reactions appeared as a cutting-edge strategy to streamline the assembly of complex structural scaffolds from naturally available precursors in an atom-, as well as time, labor- and cost-efficient way. We herein report a strategy to control cationic cyclization cascades by exploiting the ability of anchoring dynamic substrates in the active site of terpene cyclases via designed hydrogen bonding. Thereby, it is possible to induce "directed" cyclizations in contrast to established "non-stop" cyclizations (99:1) and predestinate cascade termination at otherwise catalytically barely accessible intermediates. As a result, we are able to provide efficient access to naturally widely occurring apocarotenoids, value-added flavors and fragrances in gram-scale by replacing multi-stage synthetic routes to a single step with unprecedented selectivity (>99.5 % ee) and high yields (up to 89 %).

| S-EPMC8251838 | biostudies-literature

Radical difluoromethylthiolation of aromatics enabled by visible light.

Project description:Direct introduction of a difluoromethylthio group (-SCF2H) to arenes represents an efficient route to access a valuable catalogue of organofluorines; however, to realize this transformation under metal-free and mild conditions still remains challenging and rarely reported. Herein, a metal-catalyst-free and redox-neutral innate difluoromethylthiolation method with a shelf-stable and readily available reagent, PhSO2SCF2H, under visible light irradiation is described. This light-mediated protocol successfully converts a broad spectrum of arenes and heteroarenes to difluoromethylthioethers in the absence of noble metals and stoichiometric amounts of additives.

| S-EPMC6050601 | 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