Browse
Submit Data
Databases
API
Help

Dataset Information

27 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Light-induced metal-free transformations of unactivated pyridotriazoles.

ABSTRACT: A highly efficient and practical method for incorporation of the arylmethylpyridyl moiety into diverse molecules has been developed. This method features the transition metal-free light-induced room temperature transformation of pyridotriazoles into pyridyl carbenes, which are capable of smooth arylation, X-H insertion, and cyclopropanation reactions. The synthetic usefulness of the developed method was illustrated in a facile synthesis of biologically active molecules.

SUBMITTER: Zhang Z

PROVIDER: S-EPMC6844233 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Light-induced metal-free transformations of unactivated pyridotriazoles.

Zhang Ziyan Z Yadagiri Dongari D Gevorgyan Vladimir V

Chemical science 20190725 36

A highly efficient and practical method for incorporation of the arylmethylpyridyl moiety into diverse molecules has been developed. This method features the transition metal-free light-induced room temperature transformation of pyridotriazoles into pyridyl carbenes, which are capable of smooth arylation, X-H insertion, and cyclopropanation reactions. The synthetic usefulness of the developed method was illustrated in a facile synthesis of biologically active molecules. ...[more]

PMID: 31803418

Similar Datasets

Metal-free visible-light-enabled vicinal trifluoromethyl dithiolation of unactivated alkenes.

Project description:The difunctionalization of alkenes involving a trifluoromethylthio group (SCF3) for the conversion of versatile and readily available olefins into structurally more complex molecules has been successfully studied. However, the disproportionate dithiolation of alkenes is unknown. Herein, a transition-metal-free protocol is presented for the vicinal trifluoromethylthio-thiolation of unactivated alkenes via a radical process under mild conditions with a broad substrate scope and excellent tolerance.

| S-EPMC7934782 | biostudies-literature

Transition-Metal- and Light-Free Directed Amination of Remote Unactivated C(sp3)-H Bonds of Alcohols.

Project description:Due to the great value of amino alcohols, new methods for their synthesis are in high demand. Abundant aliphatic alcohols represent the ideal feedstock for the method development toward this important motif. To date, transition-metal-catalyzed approaches for the directed remote amination of alcohols have been well established. Yet, they have certain disadvantages such as the use of expensive catalysts and limited scope. Very recently, transition-metal-free visible-light-induced radical approaches have emerged as new powerful tools for directed remote amination of alcohols. Relying on 1,5-HAT reactivity, these methods are limited to ? - or ?-amination only. Herein, we report a novel transition-metal- and visible-light-free room-temperature radical approach for remote ? -, ?-, and ?-C(sp3)-N bond formation in aliphatic alcohols using mild basic conditions and readily available diazonium salt reagents.

| S-EPMC6873700 | biostudies-literature

Transition Metal-Free 1,2-Carboboration of Unactivated Alkenes.

Project description:A method for transition metal-free 1,2-carboboration of unactivated alkenes with bis(catecholato)diboron as the boron source in combination with alkyl halides as the alkyl component is introduced. The three-component reaction proceeds via a radical pathway on a broad range of unactivated alkenes, and the 1,2-carboboration products serve as valuable synthetic building blocks. Density functional theory calculations provide insights into the mechanism.

| S-EPMC6014685 | biostudies-literature

Visible Light Induced Metal-Free Carbene <i>N</i>-Carbazolation.

Project description:Metal-free N-H functionalization reactions represent an important strategy for sustainable C-N coupling reactions. In this report, we describe the visible light photolysis of aryl diazoacetates in the presence of some N-heterocycles that enables mild, metal-free N-H functionalization reactions of carbazole and azepine heterocycles (15 examples, up to 83% yield).

| S-EPMC6900254 | biostudies-literature

A visible-light-induced, metal-free bis-arylation of 2,5-dichlorobenzoquinone.

Project description:A metal-free protocol for the direct bis-arylation of 2,5-dichlorobenzoquinone with aryldiazonium salts is reported. The reactive salts are generated in situ and converted to radicals through irradiation with visible light. Reaction products precipitate from the solvent, eliminating the need for purification and thus providing a novel green method for the synthesis of versatile bis-electrophiles.

| S-EPMC8450952 | biostudies-literature

Metal-free Regioselective Hydrochlorination of Unactivated Alkenes via a Combined Acid Catalytic System.

Project description:A combined acid HCl/DMPU-acetic acid catalytic system was used in the hydrochlorination of a wide range of unactivated alkenes. This hydrochlorination strategy is remarkably greener than previous reported methods in terms of high atom efficiency, no toxic waste generated and metal-free process. The higher efficiency, compared with other commercially available HCl reagents, was augmented by the good regioselectivity and functionality tolerance found. A stepwise mechanism for this hydrochlorination process was proposed based on kinetic studies.

| S-EPMC5937714 | biostudies-literature

Trifluoromethanesulfonyl azide as a bifunctional reagent for metal-free azidotrifluoromethylation of unactivated alkenes.

Project description:Vicinal trifluoromethyl azides have widespread applications in organic synthesis and drug development. However, their preparation is generally limited to transition-metal-catalyzed three-component reactions. We report here a simple and metal-free method that rapidly provides these building blocks from abundant alkenes and trifluoromethanesulfonyl azide (N3SO2CF3). This unprecedented two-component reaction employs readily available N3SO2CF3 as a bifunctional reagent to concurrently incorporate both CF3 and N3 groups, which avoids the use of their expensive and low atom economic precursors. A wide range of functional groups, including bio-relevant heterocycles and amino acids, were tolerated. Application of this method was further demonstrated by scale-up synthesis (5 mmol), product derivatization to CF3-containing medicinal chemistry motifs, as well as late-stage modification of natural product and drug derivatives.

| S-EPMC8179360 | biostudies-literature

Metal-free alcohol-directed regioselective heteroarylation of remote unactivated C(sp3)-H bonds.

Project description:Construction of C-C bonds via alkoxy radical-mediated remote C(sp3)-H functionalization is largely unexplored, as it is a formidable challenge to directly generate alkoxy radicals from alcohols due to the high bond dissociation energy (BDE) of O-H bonds. Disclosed herein is a practical and elusive metal-free alcohol-directed heteroarylation of remote unactivated C(sp3)-H bonds. Phenyliodine bis(trifluoroacetate) (PIFA) is used as the only reagent to enable the coupling of alcohols and heteroaryls. Alkoxy radicals are readily generated from free alcohols under the irradiation of visible light, which trigger the regioselective hydrogen-atom transfer (HAT). A wide range of functional groups are compatible with the mild reaction conditions. Two unactivated C-H bonds are cleaved and one new C-C bond is constructed during the reaction. This protocol provides an efficient strategy for the late-stage functionalization of alcohols and heteroaryls.

| S-EPMC6104081 | biostudies-other

Metal-free visible-light-induced hydroxy-perfluoroalkylation of conjugated olefins using enamine catalyst.

Project description:We developed a simple and sustainable method for the hydroxy-perfluoroalkylation of electron-deficient conjugated olefins and styrenes. In this protcol, in situ generated enamine forms electron-donor-accepter (EDA) complexes with perfluoroalkyl iodide, and reaction proceed with visible-light irradiation. Tertiary amine also interacts with perfluoroalkyl iodide via halogen-bonding, promoting the perfluoroalkyl radical generation. This reaction does not require any transition-metal or photoredox catalyst, and gaseous oxygen is used as the green hydroxy source. Moreover, various commercially available substrates and perfluoroalkyl iodides were tolerated, affording the desired hydroxy-perfluoroalkylated products in good to moderate yields (>50 examples, up to 90%).

| S-EPMC9667149 | biostudies-literature

A general metal-free approach for the stereoselective synthesis of C-glycals from unactivated alkynes.

Project description:A novel metal-free strategy for a rapid and ?-selctive C-alkynylation of glycals was developed. The reaction utilizes TMSOTf as a promoter to generate in situ trimethylsilylacetylene for C-alkynylation. Thanks to this methodology, we can access C-glycosides in a single step from a variety of acetylenes , i.e., arylacetylenes and most importantly aliphatic alkynes.

| S-EPMC4273296 | 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