Browse
Submit Data
Databases
API
Help

Dataset Information

19 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Electrochemical C-C bond cleavage of cyclopropanes towards the synthesis of 1,3-difunctionalized molecules.

ABSTRACT: Electrochemistry has a lot of inherent advantages in organic synthesis and many redox reactions have been achieved under electrochemical condition. However, the electrochemical C-C bond cleavage and functionalization reactions are less studied. Here we develop electrochemical C-C bond cleavage and 1,3-difuntionalization of arylcyclopropanes under catalyst-free and external-oxidant-free conditions. 1,3-difluorination, 1,3-oxyfluorination and 1,3-dioxygenation of arylcyclopropanes are achieved with a high chemo- and regioselectivity by the strategic choice of nucleophiles. This protocol has good functional groups tolerance and can be scaled up. Mechanistic studies demonstrate that arylcyclopropane radical cation obtained from the anode oxidation and the subsequently generated benzyl carbonium are the key intermediates in this transformation. This development provides a scenario for constructing 1,3-difunctionalized molecules.

SUBMITTER: Peng P

PROVIDER: S-EPMC8144616 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Towards selective electrochemical conversion of glycerol to 1,3-propanediol.

Project description:1,3-propanediol (1,3-PD) is a bulk chemical with myriad applications in polymers, lubricants, cosmetics, foods industries and in the synthesis of heterocyclic compounds. Current commercial production of 1,3-PD involves a thermocatalytic process using acrolein (DuPont) and ethylene oxide (Shell) as starting feedstock. These feedstocks are petroleum-based and there are many efforts at using glycerol as low cost biomass-derived feedstock for 1,3-PD production. A number of catalyst designs and bacterial & fungal strains are being explored for respective catalytic and fermentation routes to glycerol-to-1,3-PD. However, the electrochemical method received little attention for the purpose. In this work, in order to explore the possibility of using partly refined glycerol byproduct of biodiesel production as feedstock, we investigated conversion and 1,3-PD selectivity of glycerol electrolysis in chloride media. We demonstrated selective glycerol-to-1,3-PD conversion using Pt or RuO2-based dsa as anode and Zn or Pb as cathode in NaCl and KCl at pH 1. This electrochemical glycerol-to-1,3-PD conversion is not only green, it is a potential process network loop between biodiesel production and chlor-alkali industry.

| S-EPMC9078992 | biostudies-literature

Dicationic ring-opening reactions of trans-2-phenylcyclopropylamine·HCl: electrophilic cleavage of the distal (C2-C3) bond of cyclopropanes.

Project description:Electrophilic ring opening of trans-2-phenylcyclopropylamine·HCl occurs at the distal (C2-C3) bond. This is consistent with weakening of the distal bond by the σ-withdrawing ammonium group and charge-charge repulsive effects in the transition state.

| S-EPMC5333643 | biostudies-literature

Electrochemical Synthesis of Fluorinated Orthoesters from 1,3-Benzodioxoles.

Project description:A scalable, dehydrogenative, and electrochemical synthesis of novel highly fluorinated orthoesters is reported. This protocol provides easy and direct access to a wide variety of derivatives, using a very simple electrolysis setup. These compounds are surprisingly robust towards base and acid with an unusual high lipophilicity, making them interesting motifs for potentially active compounds in medicinal chemistry or agro applications. The use of electricity enables a safe and environmentally benign chemical transformation as only electrons serve as oxidants.

| S-EPMC6718074 | biostudies-literature

Catalytic Enantioselective Synthesis of α-Difunctionalized Cyclic Sulfones.

Project description:As saturated heterocyclic building blocks become increasingly popular in medicinal chemistry and drug discovery programs, expansion of the synthetic toolkit to novel stereofunctionalized heterocycles is a priority. Herein, we report the development of a palladium-catalyzed decarboxylative asymmetric allylic alkylation reaction to access a broad range of enantioenriched α-difunctionalized 5- and 6-membered sulfones from easily accessible racemic starting materials. The allylic alkylation step was found to occur with high levels of enantioselectivity as a result of a palladium-mediated dynamic kinetic resolution of E/Z enolate intermediates. This methodology paves the way to hitherto unexplored stereodefined cyclic sulfones for medicinal chemistry applications.

| S-EPMC9490805 | biostudies-literature

Facile cleavage of C-C bond: conversion of pyrane derivative to 1,3-oxazin derivative.

Project description:A cascade reaction that involves a unique C-C bond cleavage has been discovered. This protocol affords an unusual and facile method for the synthesis of 1,3-oxazin derivatives under mild conditions.

| S-EPMC7111841 | biostudies-literature

Amide bond cleavage: acceleration due to a 1,3-diaxial interaction with a carboxylic acid.

Project description:To independently assess the contribution of ground-state pseudoallylic strain to the enormous rates of amide bond cleavage in tertiary amide derivatives of Kemp's triacid, we have studied four amide derivatives of (1alpha-3alpha-5beta)-5-tert-butyl-1,3-cyclohexanedicarboxylic acid. Our results demonstrate that absent pseudoallylic strain, a 1,3-diaxial interaction of an amide with a carboxylic acid leads to only a 2400-fold increase in the rate of amide bond cleavage as compared with the rate of hydrolysis of an unactivated peptide bond.

| S-EPMC2518966 | biostudies-literature

Rhodium-catalysed selective C-C bond activation and borylation of cyclopropanes.

Project description:Transition metal (TM)-catalysed directed hydroboration of aliphatic internal olefins which facilitates the construction of complex alkylboronates is an essential synthetic methodology. Here, an efficient method for the borylation of cyclopropanes involving TM-catalysed directed C-C activation has been developed. Upon exposure to neutral Rh(i)-catalyst systems, N-Piv-substituted cyclopropylamines (CPAs) undergo proximal-selective hydroboration with HBpin to provide valuable γ-amino boronates in one step which are otherwise difficult to synthesize by known methods. The enantioenriched substrates can deliver chiral products without erosion of the enantioselectivities. Versatile synthetic utility of the obtained γ-amino boronates is also demonstrated. Experimental and computational mechanistic studies showed the preferred pathway and the origin of this selectivity. This study will enable the further use of CPAs as valuable building blocks for the tunable generation of C-heteroatom or C-C bonds through selective C-C bond activation.

| S-EPMC8179453 | biostudies-literature

One-Pot Synthesis of Asymmetrically Difunctionalized Oligomaltosides by Cyclodextrin Ring Opening.

Project description:The synthesis of pure difunctionalized hexa-, hepta- and octamaltosides was performed by one-pot chemical reaction from perbenzoylated cyclodextrin. Oligomaltosides with azide, propargyl or allyl on reducing end and an unprotected hydroxyl group on non-reducing end were obtained from perbenzoylated α-, β- and γ-cyclodextrin with 12 to 48 % yields.

| S-EPMC8080284 | biostudies-literature

Cu-catalyzed C-C bond formation of vinylidene cyclopropanes with carbon nucleophiles.

Project description:The development of Cu-catalyzed addition of carbon nucleophiles to vinylidene cyclopropanes was reported. The reactions with 1,1-bisborylmethane provided homopropargylic boronate products by forming a C-C bond at the terminal carbon atom of the allene moiety of vinylidene cyclopropanes. Alkynyl boronates are also suitable nucleophile precursors in reactions with vinylidene cyclopropanes, and skipped diynes were obtained in high yields. In addition, the Cu-enolate generated from the initial addition of nucleophilic copper species to vinylidene cyclopropanes can be intercepted by an external electrophile. As such, vinylidene cyclopropane serves as a linchpin to connect a nucleophile and an electrophile by forming two carbon-carbon bonds sequentially.

| S-EPMC7020789 | biostudies-literature

Ring-Opening 1,3-Aminochalcogenation of Donor-Acceptor Cyclopropanes: A Three-Component Approach.

Project description:A 1,3-aminothiolation was realized by reacting 2-substituted cyclopropane 1,1-dicarboxylates with sulfonamides and N-(arylthio)succinimides. Under Sn(OTf)2 catalysis the transformation proceeded smoothly to the corresponding ring-opened products bearing the sulfonamide in the 1-position next to the donor and the arylthio residue in the 3-position next to the acceptor. The procedure was extended to the corresponding selenium analogues by employing N-(phenylseleno)succinimides as an electrophilic selenium source.

| S-EPMC6771889 | biostudies-other

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