Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Synthesis of 3-Amino-1-benzothiophene-1,1-diones by Alkyne Directed Hydroarylation and 1/N?3/C-Sulfonyl Migration.

ABSTRACT: A completely regioselective and highly stereoselective palladium-catalyzed intramolecular hydroarylation of arenesulfonyl ynamines to benzothiazoles was developed. The presence of an electron-withdrawing group on the triple bond of the sulfonyl ynamine was crucial for the success of the reaction and our mechanistic studies suggest an alkyne-directed 5-exo-dig cyclization pathway. The products easily underwent photoinduced rearrangement to 3-amino-1-benzothiophene-1,1-diones (up to 35?% yields after two steps).

SUBMITTER: Bernar I

PROVIDER: S-EPMC6220774 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Synthesis of 3-Amino-1-benzothiophene-1,1-diones by Alkyne Directed Hydroarylation and 1/N→3/C-Sulfonyl Migration.

Bernar Ivan I Blanco-Ania Daniel D Stok Sophie J SJ Sotorríos Lia L Gómez-Bengoa Enrique E Rutjes Floris P J T FPJT

European journal of organic chemistry 20181010 39

A completely regioselective and highly stereoselective palladium-catalyzed intramolecular hydroarylation of arenesulfonyl ynamines to benzothiazoles was developed. The presence of an electron-withdrawing group on the triple bond of the sulfonyl ynamine was crucial for the success of the reaction and our mechanistic studies suggest an alkyne-directed 5-<i>exo</i>-dig cyclization pathway. The products easily underwent photoinduced rearrangement to 3-amino-1-benzothiophene-1,1-diones (up to 35 % yi ...[more]

PMID: 30443160

Similar Datasets

Gold-catalyzed post-Ugi alkyne hydroarylation for the synthesis of 2-quinolones.

Project description:A series of propargylamides containing an electron-rich benzene ring was prepared through the Ugi reaction of 3,5-dimethoxyaniline with various propiolic acids, aldehydes and isocyanides. Subjecting these adducts to a gold-catalyzed intramolecular alkyne hydroarylation process allowed to efficiently construct the 2-quinolone core bearing a branched substituent on the nitrogen atom.

| S-EPMC6204774 | biostudies-literature

The synthesis and structures of 1,1'-bis(sulfonyl)ferrocene derivatives.

Project description:A series of 1,1'-bis(sulfonyl)ferrocene compounds were produced via the 1,1'-bis(sulfonate)ferrocene ammonium salt. This compound can be readily converted to 1,1' bis(sulfonylchloride)ferrocene. By varying stoichiometry and reaction times, both mono- and bis-sulfonamide derivatives can be synthesized. All new compounds presented in this report have been structurally characterized. The structures of the bis-sulfonamide systems are similar to the well-studied bis(amide) ferrocene compounds. Intermolecular hydrogen bonding is observed, typically between NH and SO groups of neighboring sulfonamides. However in the bis(GABA) derivative, intermolecular NH to CO hydrogen bonding interactions are present.

| S-EPMC5629003 | biostudies-literature

Imidazolidine Hydride Donors in Palladium-Catalyzed Alkyne Hydroarylation.

Project description:Aldehyde-derived imidazolidines participate as hydride donors in intramolecular reductive Heck-type reactions. N,N'-Diphenylimidazolidines prepared from ortho-alkynyl benzaldehydes underwent regio- and stereoselective palladium-catalyzed hydroarylation followed by formal 1,5-hydride transfer and reductive elimination to afford substituted alkenes and imidazolium moieties, the latter conveniently converted in situ to ring-opened benzanilides to simplify product isolation. Internal alkynes were converted to trisubstituted alkenes via a syn hydroarylation process, while a terminal alkyne was converted to a cis alkene via a formal trans hydroarylation reaction. Benzanilide products could be converted to carboxylic acid derivatives under basic conditions, resulting in the net conversion of alkynyl aldehydes to alkenyl carboxylic acids. A styrene derivative with an attached N,N'-dimethylbenzimidazoline hydride donor was also found to undergo an analogous hydroarylation/benzimidazoline oxidation to give a diarylethane product.

| S-EPMC9490851 | biostudies-literature

Synthesis and Photophysical Properties of β-Alkenyl-Substituted BODIPY Dyes by Indium(III)-Catalyzed Intermolecular Alkyne Hydroarylation.

Project description:A new atom-economical synthesis of β-alkenyl-substituted BODIPYs via indium(III)-catalyzed intermolecular alkyne hydroarylation with meso-substituted BODIPYs is described. While catalysis with InI3 allows the double β-functionalization of BODIPY, resulting in regioselectively branched β,β'-disubstituted alkenyl BODIPYs, catalytic InCl3 enables the formation of linear β-substituted alkenyl BODIPYs. Subsequent In(III)-catalyzed intermolecular alkyne hydroarylation allows the synthesis of unsymmetrical push-pull BODIPY derivatives. Therefore, indium catalysis offers complementary regioselectivity in good chemical yields and functional group tolerance. The resulting BODIPY dyes displayed bathochromically shifted absorption and emission according to the electron-nature of the substituents in the alkenyl moiety with high molar extinction coefficients (ε up to 88,200 M-1 cm-1) and quantum yields (0.14-0.96).

| S-EPMC11002825 | biostudies-literature

New 1,1'-Ferrocene Bis(sulfonyl) Reagents.

Project description:Several new 1,1'-bis(sulfonyl)ferrocenes designed for the synthesis of sulfonamide linked biological conjugates have been prepared. 1,1'-Bis(sulfonylbromide)ferrocene can be produced from the corresponding sulfonylchloride via a bis(sulfonylhydrazide) intermediate. Bis(sulfonyl-N-hydroxybenzotriazole)ferrocene can also be synthesized from the sulfonyl chloride, and reaction of glycine methyl ester with the sulfonyl chloride affords a [3]ferrocenophane complex. All new compounds have been structurally characterized by X-ray crystallography.

| S-EPMC5758046 | biostudies-literature

Stereoselective Synthesis of Quaternary Pyrrolidine-2,3-diones and β-Amino Acids.

Project description:A facile, diastereoselective synthesis of highly substituted pyrrolidine-2,3-diones is reported, along with the one-step conversion of these heterocycles to novel β-amino acids and further functionalized derivatives. This method involves an unusually mild, one-pot, three-component cyclization/allylation followed by a Claisen rearrangement to provide unusual pyrrolidinone products that are densely functionalized and contain an all-carbon quaternary stereocenter. The reported reaction sequence is operationally simple, exquisitely diastereoselective, and provides gram-scale access to valuable heterocyclic scaffolds and β-amino acids not readily accessible via existing approaches.

| S-EPMC5540151 | biostudies-literature

Sulfoxide-directed metal-free cross-couplings in the expedient synthesis of benzothiophene-based components of materials.

Project description:A metal-free approach combining sulfoxide-directed metal-free C-H cross-couplings with tuneable electrophile-mediated heterocyclizations and carbocyclative dimerizations, allows expedient access to benzothiophene-based systems that are components of important materials or are proven organic materials in their own right. As benzothiophene-based materials are typically prepared using Pd-catalyzed cross-coupling processes, our approach allows potential issues of metal cost and supply, and metal-contamination of products, to be avoided.

| S-EPMC5975836 | biostudies-literature

The synthesis of brominated-boron-doped PAHs by alkyne 1,1-bromoboration: mechanistic and functionalisation studies.

Project description:The synthesis of a range of brominated-B n -containing (n = 1, 2) polycyclic aromatic hydrocarbons (PAHs) is achieved simply by reacting BBr3 with appropriately substituted alkynes via a bromoboration/electrophilic C-H borylation sequence. The brominated-B n -PAHs were isolated as either the borinic acids or B-mesityl-protected derivatives, with the latter having extremely deep LUMOs for the B2-doped PAHs (with one example having a reduction potential of E 1/2 = -0.96 V versus Fc+/Fc, Fc = ferrocene). Mechanistic studies revealed the reaction sequence proceeds by initial alkyne 1,1-bromoboration. 1,1-Bromoboration also was applied to access a number of unprecedented 1-bromo-2,2-diaryl substituted vinylboronate esters directly from internal alkynes. Bromoboration/C-H borylation installs useful C-Br units onto the B n -PAHs, which were utilised in Negishi coupling reactions, including for the installation of two triarylamine donor (D) groups onto a B2-PAH. The resultant D-A-D molecule has a low optical gap with an absorption onset at 750 nm and emission centered at 810 nm in the solid state.

| S-EPMC8157679 | biostudies-literature

Synthesis and Reactivity of a Bis-Strained Alkyne Derived from 1,1'-Biphenyl-2,2',6,6'-tetrol.

Project description:The novel "double strained alkyne" 3 has been prepared and evaluated in strain-promoted azide-alkyne cycloaddition reactions with azides. The X-ray crystallographic structure of 3, which was prepared in one step from 1,1'-biphenyl-2,2',6,6'-tetrol 4, reveals the strained nature of the alkynes. Dialkyne 3 undergoes cycloaddition reactions with a number of azides, giving mixtures of regiosiomeric products in excellent yields. The monoaddition products were not observed or isolated from the reactions, suggesting that the second cycloaddition proceeds at a faster rate than the first, and this is supported by molecular modeling studies. Dialkyne 3 was successfully employed for "peptide stapling" of a p53-based diazido peptide, whereby two azides are bridged to give a product with a stabilized conformation.

| S-EPMC6648819 | biostudies-literature

Synthesis of benzothiophene and indole derivatives through metal-free propargyl-allene rearrangement and allyl migration.

Project description:An efficient base-catalyzed protocol for the synthesis of benzothiophene is described. The reaction proceeds via base-promoted propargyl-allenyl rearrangement followed by cyclization and allyl migration. Phosphine-substituted indoles can be synthesized by a similar strategy.

| S-EPMC5629416 | 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