Browse
Submit Data
Databases
API
Help

Dataset Information

4 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Intramolecular carbolithiation of N-allyl-ynamides: an efficient entry to 1,4-dihydropyridines and pyridines - application to a formal synthesis of sarizotan.

ABSTRACT: We have developed a general synthesis of polysubstituted 1,4-dihydropyridines and pyridines based on a highly regioselective lithiation/6-endo-dig intramolecular carbolithiation from readily available N-allyl-ynamides. This reaction, which has been successfully applied to the formal synthesis of the anti-dyskinesia agent sarizotan, further extends the use of ynamides in organic synthesis and further demonstrates the synthetic efficiency of carbometallation reactions.

SUBMITTER: Gati W

PROVIDER: S-EPMC3557957 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

An umpolung approach to the hydroboration of pyridines: a novel and efficient synthesis of N-H 1,4-dihydropyridines.

Project description:The first inverse hydroboration of pyridine with a diboron(4) compound and a proton source has been realized under simple basic and catalyst-free conditions. This process consists of a formal boryl anion addition to pyridine, which produces an N-boryl pyridyl anion complex, and the subsequent protonation of the anion complex. This process enables a simple and efficient method for the synthesis of multi-substituted N-H 1,4-dihydropyridine (1,4-DHP) derivatives that are difficult to prepare using established methods. Furthermore, this method allows for facile preparation of 4-deuterated 1,4-DHPs from an easily accessible deuterium ion source. This inverse hydroboration reaction represents a new mode for pyridine functionalization.

| S-EPMC8145361 | biostudies-literature

An intramolecular [2 + 2] cycloaddition of ketenimines via palladium-catalyzed rearrangements of N-allyl-ynamides.

Project description:A cascade of Pd-catalyzed N-to-C allyl transfer-intramolecular ketenimine-[2 + 2] cycloadditions of N-allyl ynamides is described. This tandem sequence is highly stereoselective and the [2 + 2] cycloaddition could be rendered in a crossed or fused manner depending on alkene substitutions, leading to bridged and fused bicycloimines.

| S-EPMC3426664 | biostudies-literature

Ammonium metavanadate (NH4VO3): a highly efficient and eco-friendly catalyst for one-pot synthesis of pyridines and 1,4-dihydropyridines.

Project description:In this study, we reported the ammonium metavanadate (NH4VO3) as an efficient, cost-effective, and mild catalyst for the synthesis of substituted pyridines via a one-pot pseudo four-component reaction. Furthermore, we investigated Hantzsch 1,4-dihydropyridines (1,4-DHPs) synthesis and oxidation of 1,4-DHPs to their corresponding pyridines. The present approach offers a rapid methodology for accessing various pyridines with broad functional group tolerance and good yields using NH4VO3 catalyst as a green catalyst.

| S-EPMC9372032 | biostudies-literature

Application of novel nanomagnetic metal-organic frameworks as a catalyst for the synthesis of new pyridines and 1,4-dihydropyridines via a cooperative vinylogous anomeric based oxidation.

Project description:Herein, a new magnetic metal-organic frameworks based on Fe3O4 (NMMOFs) with porous and high surface area materials were synthesized. Then, NMMOFs were characterized by FT-IR, XRD, SEM, elemental mapping, energy dispersive X-ray (EDS), TG, DTG, VSM, and N2 adsorption-desorption isotherms (BET). Fe3O4@Co(BDC)-NH2 as a magnetic porous catalyst was applied for synthesis of novel fused pyridines and 1,4-dihydropyridines with pyrazole and pyrimidine moieties as suitable drug candidates under ultrasonic irradiation. The significant advantages of the presented methodology are mild, facile workup, high yields, short reaction times, high thermal stability, and reusability of the described NMMOFs catalyst.

| S-EPMC7935861 | biostudies-literature

Synthesis of amidines using N-allyl ynamides. A palladium-catalyzed allyl transfer through an ynamido-pi-allyl complex.

Project description:A de novo transformation of N-allyl-N-sulfonyl ynamides to amidines is described featuring a palladium-catalyzed N-to-C allyl transfer via ynamido-palladium-pi-allyl complexes.

| S-EPMC2683379 | biostudies-literature

Carbocyclization cascades of allyl ketenimines via aza-Claisen rearrangements of N-phosphoryl-N-allyl-ynamides.

Project description:A series of carbocyclization cascades of allyl ketenimines initiated through a thermal aza-Claisen rearrangement of N-phosphoryl-N-allyl ynamides is described. Interceptions of the cationic intermediate via Meerwein-Wagner rearrangements and polyene-type cyclizations en route to fused bi- and tricyclic frameworks are featured.

| S-EPMC3321125 | biostudies-literature

Divergent C-H Insertion-Cyclization Cascades of N-Allyl Ynamides.

Project description:Gold carbene reactivity patterns were accessed by ynamide insertion into a C(sp(3) )H bond. A substantial increase in molecular complexity occurred through the cascade polycyclization of N-allyl ynamides to form fused nitrogen-heterocycle scaffolds. Exquisite selectivity was observed despite several competing pathways in an efficient gold-catalyzed synthesis of densely functionalized C(sp(3) )-rich polycycles and a copper-catalyzed synthesis of fused pyridine derivatives. The respective gold-keteniminium and ketenimine activation pathways have been explored through a structure-reactivity study, and isotopic labeling identified turnover-limiting CH bond-cleavage in both processes.

| S-EPMC4832826 | biostudies-literature

b-Annulated 1,4-dihydropyridines as Notch inhibitors.

Project description:The Notch signaling pathway is involved in cell proliferation and differentiation, and has been recognized as an active pathway in regenerating tissue and cancerous cells. Notch signaling inhibition is considered a viable approach to the treatment of a variety of conditions including colorectal cancer, pancreatic cancer, breast cancer and metastatic melanoma. The discovery that the b-annulated dihydropyridine FLI-06 (1) is an inhibitor of the Notch pathway with an EC50 ≈ 2.5 μM prompted us to screen a library of related analogs. After structure activity studies were conducted, racemic compound 7 was identified with an EC50 = 0.36 μM. Synthesis of individual enantiomers provided (+)-7 enantiomer with an EC50 = 0.13 μM, or about 20-fold the potency of 1.

| S-EPMC6261437 | biostudies-literature

Arylative Intramolecular Allylation of Ketones with 1,3-Enynes Enabled by Catalytic Alkenyl-to-Allyl 1,4-Rhodium(I) Migration.

Project description:Alkenyl-to-allyl 1,4-rhodium(I) migration enables the generation of nucleophilic allylrhodium(I) species by remote C-H activation. This new mode of reactivity was employed in the diastereoselective reaction of arylboron reagents with substrates containing a 1,3-enyne tethered to a ketone, to give products containing three contiguous stereocenters. The products can be obtained in high enantioselectivities using a chiral sulfur-alkene ligand.

| S-EPMC5488243 | biostudies-literature

Highly Efficient Electrocarboxylation Method to Synthesize Novel Acid Derivatives of 1,4-Dihydropyridines and to Study Their Antimicrobial Activity.

Project description:1,4-Dihydropyridines (1,4-DHPs) hold a top-notch position in the pharmaceutical world due to a broader spectrum of applications, whereas the carboxylic moiety has been an integral part of the physiological world, effective food preservatives, and antimicrobial agents. Seeking the enormous potential and applications of these two classes, we worked to combine these to synthesize 2,2'-[3,5-bis(ethoxycarbonyl)-4-phenyl-1,4-dihydropyridine-2,6-diyl]diacetic acid the novel dicarboxylic derivatives of 1,4-DHP (9a-k) achieved via the electro-carboxylation of tetrasubstituted-1,4-dihydropyridines (8a-k) derivatives using Mg-Pt electrodes in an undivided cell. The targeted compounds were established by 1H, 13C NMR, IR, and ESI-MS. Further, the synthesized compounds show excellent resistance against various microbes and the activity increased 2-3 folds after the introduction of acid groups. Compound 9b (against E. coli, S. aureus, B. subtilis, A. niger, and P. glabrum), 9d (against E. coli, K. pneumonia, S. aureus, A. janus, and F. oxysporum), 9f (against E. coli and P. fluorescens), and 9k (against F. oxysporum and P. glabrum) were found to be highly active at 4 μg/mL with reference to standard amoxicillin and fluconazole. Further, the present synthetic protocol would open new gates for other researchers to develop new molecules by bioisosteres of these substrates.

| S-EPMC9097205 | 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