Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Room Temperature Activation of Aryloxysulfonyl Azides by [Co(II)(TPP)] for Selective Radical Aziridination of Alkenes via Metalloradical Catalysis.

ABSTRACT: Aryloxysulfonyl azides can be effectively activated by commercially available cobalt(II) complex of meso-tetraphenylporphyrin ([Co(TPP)]) at room temperature under neutral and nonoxidative conditions for selective radical aziridination of alkenes via metalloradical catalysis. The [Co(TPP)]-catalyzed radical aziridination system is suitable for different combinations of olefin substrates and aryloxysulfonyl azides, producing various N-aryloxysulfonyl aziridine derivatives in good to excellent yields. In addition to generating the environmentally benign N2 as the only byproduct, this Co(II)-based metalloradical aziridination process features mild reaction conditions and operational simplicity.

SUBMITTER: Subbarayan V

PROVIDER: S-EPMC4484885 | biostudies-literature | 2015 Jun

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Room Temperature Activation of Aryloxysulfonyl Azides by [Co(II)(TPP)] for Selective Radical Aziridination of Alkenes via Metalloradical Catalysis.

Subbarayan Velusamy V Jin Li-Mei LM Xin Cui C Zhang X Peter XP

Tetrahedron letters 20150601 23

Aryloxysulfonyl azides can be effectively activated by commercially available cobalt(II) complex of <i>meso</i>-tetraphenylporphyrin ([Co(TPP)]) at room temperature under neutral and nonoxidative conditions for selective radical aziridination of alkenes via metalloradical catalysis. The [Co(TPP)]-catalyzed radical aziridination system is suitable for different combinations of olefin substrates and aryloxysulfonyl azides, producing various <i>N</i>-aryloxysulfonyl aziridine derivatives in good to ...[more]

PMID: 26139944

Similar Datasets

Intramolecular Radical Aziridination of Allylic Sulfamoyl Azides by Cobalt(II)-Based Metalloradical Catalysis: Effective Construction of Strained Heterobicyclic Structures.

Project description:Cobalt(II)-based metalloradical catalysis (MRC) has been successfully applied for effective construction of the highly strained 2-sulfonyl-1,3-diazabicyclo[3.1.0]hexane structures in high yields through intramolecular radical aziridination of allylic sulfamoyl azides. The resulting [3.1.0] bicyclic aziridines prove to be versatile synthons for the preparation of a diverse range of 1,2- and 1,3-diamine derivatives by selective ring-opening reactions. As a demonstration of its application for target synthesis, the metalloradical intramolecular aziridination reaction has been incorporated as a key step for efficient synthesis of a potent neurokinin?1 (NK1 ) antagonist in 60?% overall yield.

| S-EPMC5014589 | biostudies-literature

Synthesis of chiral N-phosphoryl aziridines through enantioselective aziridination of alkenes with phosphoryl azide via Co(II)-based metalloradical catalysis.

Project description:The Co(II) complex of a new D 2-symmetric chiral porphyrin 3,5-DiMes-QingPhyrin, [Co(P6)], can catalyze asymmetric aziridination of alkenes with bis(2,2,2-trichloroethyl)phosphoryl azide (TcepN3) as a nitrene source. This new Co(II)-based metalloradical aziridination is suitable for different aromatic olefins, producing the corresponding N-phosphorylaziridines in good to excellent yields (up to 99%) with moderate to high enantioselectivities (up to 85% ee). In addition to mild reaction conditions and generation of N2 as the only byproduct, this new metalloradical catalytic system is highlighted with a practical protocol that operates under neutral and non-oxidative conditions.

| S-EPMC4077377 | biostudies-literature

Asymmetric Radical Cyclopropanation of Alkenes with In Situ-Generated Donor-Substituted Diazo Reagents via Co(II)-Based Metalloradical Catalysis.

Project description:Donor-substituted diazo reagents, generated in situ from sulfonyl hydrazones in the presence of base, can serve as suitable radical precursors for Co(II)-based metalloradical catalysis (MRC). The cobalt(II) complex of D2-symmetric chiral porphyrin [Co(3,5-DitBu-Xu(2'-Naph)Phyrin)] is an efficient metalloradical catalyst that is capable of activating different N-arylsulfonyl hydrazones for asymmetric radical cyclopropanation of a broad range of alkenes, affording the corresponding cyclopropanes in high yields with effective control of both diastereo- and enantioselectivity. This Co(II)-based metalloradical system represents the first catalytic protocol that can effectively utilize donor-type diazo reagents for asymmetric olefin cyclopropanation.

| S-EPMC5266645 | biostudies-literature

Selective Radical Amination of Aldehydic C(sp2)-H Bonds with Fluoroaryl Azides via Co(II)-Based Metalloradical Catalysis: Synthesis of N-Fluoroaryl Amides from Aldehydes under Neutral and Nonoxidative Conditions.

Project description:The Co(II) complex of the D2h-symmetric amidoporphyrin 3,5-Di t Bu-IbuPhyrin, [Co(P1)], has proven to be an effective metalloradical catalyst for intermolecular amination of C(sp2)-H bonds of aldehydes with fluoroaryl azides. The [Co(P1)]-catalyzed process can employ aldehydes as the limiting reagents and operate under neutral and non-oxidative conditions, generating nitrogen gas as the only byproduct. The metalloradical aldehydic C-H amination is suitable for different combinations of aldehydes and fluoroaryl azides, producing the corresponding N-fluoroaryl amides in good to excellent yields. A series of mechanistic studies support a stepwise radical mechanism for the Co(II)-catalyzed intermolecular C-H amination.

| S-EPMC4111259 | biostudies-literature

Metalloradical activation of ?-formyldiazoacetates for the catalytic asymmetric radical cyclopropanation of alkenes.

Project description:For the first time, ?-formyldiazoacetates have been successfully applied for the asymmetric cyclopropanation of alkenes via Co(ii)-based metalloradical catalysis. The cobalt(ii) complex of the D2-symmetric chiral amidoporphyrin [Co(3,5-Di t Bu-ChenPhyrin)] is an effective metalloradical catalyst that can activate ?-formyldiazoacetates to cyclopropanate both aromatic and aliphatic olefins with varied electronic properties, affording the synthetically useful 1,1-cyclopropaneformylesters in high yields with both high diastereo- and enantioselectivity.

| S-EPMC5605771 | biostudies-literature

Mild, Efficient, and Metal-Free Radical 1,2-Dithiocyanation of Alkynes and Alkenes at Room Temperature.

Project description:A transition metal-free process has been reported for 1,2-dithiocyanation of alkynes in the presence of sodium persulfate and potassium thiocyanate reagent combination in a short reaction time under ambient air. Styrene derivatives are equally applicable under the same reaction conditions. Monothiocyanated vinyl derivatives were also synthesized from 2-ethynylpyridine and dimethyl acetylene dicarboxylate. The reaction proceeds by the radical/polar pathway as evidenced from our experiments and literature. After removal of the solvent from the reaction mixture by evaporation, the crude product was purified without conventional workup.

| S-EPMC6644369 | biostudies-literature

Asymmetric Radical Bicyclization of Allyl Azidoformates via Cobalt(II)-Based Metalloradical Catalysis.

Project description:Cobalt(II)-based metalloradical catalysis has been successfully applied to radical bicyclization of allyl azidoformates to construct aziridine/oxazolidinone-fused bicyclic structures. The Co(II) complex of D2-symmetric chiral amidoporphyrin 3,5-DitBu-QingPhyrin has been identified as an effective metalloradical catalyst for the intramolecular radical aziridination of this type of carbonyl azides, allowing for high-yielding formation of synthetically useful chiral [3.1.0]-bicyclic aziridines with high diastereo- and enantioselectivity.

| S-EPMC5553632 | biostudies-literature

Electrochemical flow aziridination of unactivated alkenes

Project description: Not available

| S-EPMC10697417 | biostudies-literature

?-Selective Aroylation of Activated Alkenes by Photoredox Catalysis.

Project description:Late-stage synthesis of ?,?-unsaturated aryl ketones remains an unmet challenge in organic synthesis. Reported herein is a photocatalytic non-chain-radical aroyl chlorination of alkenes by a 1,3-chlorine atom shift to form ?-chloroketones as masked enones that liberate the desired enones upon workup. This strategy suppresses side reactions of the enone products. The reaction tolerates a wide array of functional groups and complex molecules including derivatives of peptides, sugars, natural products, nucleosides, and marketed drugs. Notably, addition of 2,6-di-tert-butyl-4-methyl-pyridine enhances the quantum yield and efficiency of the cross-coupling reaction. Experimental and computational studies suggest a mechanism involving PCET, formation and reaction of an ?-chloro-?-hydroxy benzyl radical, and 1,3-chlorine atom shift.

| S-EPMC6527503 | biostudies-literature

Room temperature hydrosilylation of silicon nanocrystals with bifunctional terminal alkenes.

Project description:H-terminated Si nanocrystals undergo room temperature hydrosilylation with bifunctional alkenes with distal polar moieties-ethyl ester, methyl ester, or carboxylic acids-without the aid of light or added catalyst. The passivated Si nanocrystals exhibit bright photoluminescence (PL) and disperse in polar solvents, including water. We propose a reaction mechanism in which ester or carboxylic acid groups facilitate direct nucleophilic attack of the highly curved Si surface of the nanocrystals by the alkene.

| S-EPMC3580235 | 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