Browse
Submit Data
Databases
API
Help

Dataset Information

26 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

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

ABSTRACT: 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.

SUBMITTER: Jiang H

PROVIDER: S-EPMC5553632 | biostudies-literature | 2017 Jul

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

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

Jiang Huiling H Lang Kai K Lu Hongjian H Wojtas Lukasz L Zhang X Peter XP

Journal of the American Chemical Society 20170629 27

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]-bi ...[more]

PMID: 28650659

Similar Datasets

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

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

Stereoselective Radical C-H Alkylation with Acceptor/Acceptor-Substituted Diazo Reagents via Co(II)-Based Metalloradical Catalysis.

Project description:Co(II)-based metalloradical catalysis has been, for the first time, successfully applied for asymmetric intramolecular C-H alkylation of acceptor/acceptor-substituted diazo reagents. Through the design and synthesis of a new D2-symmetric chiral amidoporphyrin as the supporting ligand, the Co(II)-based metalloradical system, which operates at room temperature, is capable of 1,5-C-H alkylation of α-methoxycarbonyl-α-diazosulfones with a broad range of electronic properties, providing the 5-membered sulfolane derivatives in high yields with excellent diastereoselectivity and enantioselectivity. In addition to complete chemoselectivity toward allylic and allenic C-H bonds, the Co(II)-based metalloradical catalysis for asymmetric C-H alkylation features a remarkable degree of functional group tolerance.

| S-EPMC4324598 | biostudies-literature

Chemoselective amination of propargylic C(sp³)-H bonds by cobalt(II)-based metalloradical catalysis.

Project description:Highly chemoselective intramolecular amination of propargylic C(sp(3))-H bonds has been demonstrated for N-bishomopropargylic sulfamoyl azides through cobalt(II)-based metalloradical catalysis. Supported by D(2h)-symmetric amidoporphyrin ligand 3,5-Di(t)Bu-IbuPhyrin, the cobalt(II)-catalyzed C-H amination proceeds effectively under neutral and nonoxidative conditions without the need of any additives, and generates N2 as the only byproduct. The metalloradical amination is suitable for both secondary and tertiary propargylic C-H substrates with an unusually high degree of functional-group tolerance, thus providing a direct method for high-yielding synthesis of functionalized propargylamine derivatives.

| S-EPMC4119425 | biostudies-literature

Stereoselective Intramolecular Cyclopropanation of ?-Diazoacetates via Co(II)-Based Metalloradical Catalysis.

Project description:Co(II) complexes of D2-symmetric chiral porphyrins have been proven to be effective metalloradical catalysts for the asymmetric intramolecular cyclopropanation of allyl ?-diazoacetates. 4-(Dimethylamino)pyridine (DMAP), through positive trans effect, plays an important role in the enhancement of the asymmetric induction for the intramolecular cyclopropanation process. This metalloradical catalytic system is suitable for cyclopropanation of allyl ?-diazoacetates with varied functional groups and substitution patterns, producing bicyclic products with complete diastereocontrol and good enantiocontrol.

| S-EPMC4043383 | biostudies-literature

Intramolecular 1,5-C(sp3)-H Radical Amination via Co(II)-Based Metalloradical Catalysis for Five-Membered Cyclic Sulfamides.

Project description:Co(II)-based metalloradical catalysis (MRC) proves effective for intramolecular 1,5-C-H amination of sulfamoyl azides under neutral and nonoxidative conditions, providing a straightforward approach to access strained 5-membered cyclic sulfamides with nitrogen gas as the only byproduct. The metalloradical amination system is applicable to different types of C(sp3)-H bonds and has a high degree of functional group tolerance. Additional features of the Co(II)-catalyzed 1,5-C-H amination include excellent chemoselectivity toward allylic and propargylic C-H bonds. The unique reactivity and selectivity profile of the Co(II)-catalyzed 1,5-C-H amination is attributed to the underlying radical mechanism of MRC.

| S-EPMC5271564 | biostudies-literature

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

Project description: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.

| S-EPMC4484885 | biostudies-literature

Next-Generation D2 -Symmetric Chiral Porphyrins for Cobalt(II)-Based Metalloradical Catalysis: Catalyst Engineering by Distal Bridging.

Project description:Novel D2 -symmetric chiral amidoporphyrins with alkyl bridges across two chiral amide units on both sides of the porphyrin plane (designated "HuPhyrin") have been effectively constructed in a modular fashion to permit variation of the bridge length. The CoII complexes of HuPhyrin, [Co(HuPhyrin)], represent new-generation metalloradical catalysts where the metal-centered d-radical is situated inside a cavity-like ligand with a more rigid chiral environment and enhanced hydrogen-bonding capability. As demonstrated with cyclopropanation and aziridination as model reactions, the bridged [Co(HuPhyrin)] functions notably different from the open catalysts, exhibiting significant enhancement in both reactivity and stereoselectivity. Furthermore, the length of the distal alkyl bridge can have a remarkable influence on the catalytic properties.

| S-EPMC6456056 | biostudies-literature

Stereoselective radical amination of electron-deficient C(sp3)-H bonds by Co(II)-based metalloradical catalysis: direct synthesis of α-amino acid derivatives via α-C-H amination.

Project description:The cobalt(II) complex of 3,5-Di(t)Bu-IbuPhyrin, [Co(P1)], is an effective catalyst for intramolecular amination of electron-deficient C-H bonds, including those adjacent to electron-withdrawing CO(2)R, C(O)NR(2), C(O)R, and CN groups, in excellent yields with high regio- and stereoselectivity. The [Co(P1)]-catalyzed amination system provides a direct method for the synthesis of α-amino acid derivatives from the corresponding carboxylate precursors.

| S-EPMC3466332 | 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

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