Browse
Submit Data
Databases
API
Help

Dataset Information

38 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Highly efficient synthesis and stereoselective migration reactions of chiral five-membered aza-spiroindolenines: scope and mechanistic understanding.

ABSTRACT: An Ir-catalyzed asymmetric synthesis of five-membered aza-spiroindolenines is achieved. Based on the detailed investigation of the reaction patterns of the aryl iminium migration, a one-pot asymmetric allylic dearomatization/migration sequence from racemic indole derivatives is realized, affording enantioenriched Pictet-Spengler-type products bearing an additional allylic stereogenic center adjacent to the C3 position of the indole core.

SUBMITTER: Wu QF

PROVIDER: S-EPMC6014299 | biostudies-literature | 2016 Jul

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Highly efficient synthesis and stereoselective migration reactions of chiral five-membered aza-spiroindolenines: scope and mechanistic understanding.

Wu Qing-Feng QF Zheng Chao C Zhuo Chun-Xiang CX You Shu-Li SL

Chemical science 20160329 7

An Ir-catalyzed asymmetric synthesis of five-membered aza-spiroindolenines is achieved. Based on the detailed investigation of the reaction patterns of the aryl iminium migration, a one-pot asymmetric allylic dearomatization/migration sequence from racemic indole derivatives is realized, affording enantioenriched Pictet-Spengler-type products bearing an additional allylic stereogenic center adjacent to the C3 position of the indole core. ...[more]

PMID: 30155093

Similar Datasets

Mechanistic Investigations on the Photoisomerization Reactions of Five-Membered Ring Heterocyclic Molecules Containing Sulfur and Selenium Atoms.

Project description:The restricted active space self-consistent field method in the 26-electron/27-orbital active space and the 6-311(d) basis set has been used to investigate the mechanisms of the photochemical isomerization reactions concerning the model systems of 1,2,3-thiadiazole and 1,2,3-selenadiazole. The computational works suggest that the preferred reaction paths for both 1,2,3-thiadiazole and 1,2,3-selenadiazole are as follows: reactant → Franck-Condon region → conical intersection → intermediate → transition states → photoproducts. As a result, the structures of the conical intersections, which play a decisive role in these photoisomerization reactions, are obtained. In particular, the present theoretical evidences demonstrate that the potential energy surfaces for the formation of 1,3-diradicals are quite flat. This may explain why their experimental detections are so difficult.

| S-EPMC6641236 | biostudies-literature

Stereoselective RNA Reaction with Chiral 2'-OH Acylating Agents

Project description:The reactivity of RNA 2'-OH groups with acylating agents has recently been investigated for high-yield conjugation of RNA strands. To date, only achiral molecules have been studied for this reaction, despite the complex chiral structure of RNA. Here we prepare a set of chiral acylimidazoles and study their stereoselectivity in RNA reactions. Reactions performed with unfolded and folded RNAs reveal that positional selectivity and reactivity vary widely with local RNA macro-chirality. We further document remarkable effects of chirality on reagent reactivity, identifying an asymmetric reagent with 1000-fold greater reactivity than prior achiral reagents. In addition, we identify a chiral compound with higher RNA structural selectivity than any previously reported RNA-mapping species. Further, azide-containing homologs of a chiral dimethylalanine reagent were synthesized and applied to local RNA labeling, displaying 92% yield and 16:1 diastereoselectivity. The results establish that reagent stereochemistry and chiral RNA structure are critical elements of small molecule-RNA reactions, and demonstrate new chemical strategies for selective RNA modification and probing.

2023-11-14 | GSE247565 | GEO

The reaction of potassium xanthates with five-membered cyclic carbonates: selectivity of the underlying cascade reactions and mechanistic insights.

Project description:In this paper we describe the reaction between various potassium xanthates (potassium O-methyl xanthate, potassium O-isobutyl xanthate, xanthate functionalized MPEGs, etc.) and common five-membered cyclic carbonates such as ethylene carbonate (EC) and propylene carbonate (PC). The reaction was carried out under catalyst-free conditions. Intensive evolution of both CO2 and COS and the simultaneous formation of a rich precipitate were found to be the characteristic features of the studied reaction. It was determined that the precipitate consists of various alkoxides, including potassium ethane-1,2-bis(olate) (EC-based reaction) and potassium propane-1,2-bis(olate) (PC-based reaction) and alkoxide-terminated sulfides. It was also demonstrated that the resulting liquid phase (the mother liquor) contains polyalkylene sulfides whose number average molecular weight (M n) was found to be in the range 400-550 Da and 300-400 Da for EC- and PC-based oligomers, respectively. Further studies revealed that the distribution between major products varies considerably with variation in the parameters of the reaction. Thus, by applying reduced pressure conditions and a temperature equal to 90 °C, up to 95% selectivity towards the formation of alkoxide-terminated sulfide (e.g., potassium 1,1'-thiobis(propan-2-olate)) was achieved. On the other hand, selectivity towards alkoxide formation equal to 98% was achieved for the reactions carried out in the presence of water. As a general trend, it was also established that a shift in balance between products towards the formation of sulfur-containing products (sulfides) occurs with an appropriate increase in the temperature of the reaction. Based on the obtained experimental data supplemented with quantum-chemical calculations (NBO analysis and scanning of the potential energy surface), the mechanisms of the cascade reactions underlying the formation of key intermediates and final products were also proposed.

| S-EPMC9056968 | biostudies-literature

Diels-Alder reactions of five-membered heterocycles containing one heteroatom.

Project description:Diels-Alder reactions of five-membered heterocycles containing one heteroatom with an N-arylmaleimide were studied. Cycloaddition of 2,5-dimethylfuran (4) with 2-(4-methylphenyl)maleimide (3) in toluene at 60 °C gave bicyclic adduct 5. Cycloadditions of 3 with 2,5-dimethylthiophene (11) and 1,2,5-trimethylpyrrole (14) were also studied. Interestingly, the bicyclic compound 5 cleanly rearranged, with loss of water, when treated with p-toluenesulfonic acid in toluene at 80 °C to give 4,7-dimethyl-2-p-tolylisoindoline-1,3-dione (6).

| S-EPMC4378267 | biostudies-literature

Stereoelectronic Model To Explain Highly Stereoselective Reactions of Seven-Membered-Ring Oxocarbenium-Ion Intermediates.

Project description:Nucleophilic attack on seven-membered-ring oxocarbenium ions is generally highly stereoselective. The preferred mode of nucleophilic attack forms the product in a conformation that minimizes transannular interactions, thus leading to different stereoselectivity as compared to that of reactions involving six-membered-ring oxocarbenium ions.

| S-EPMC4811184 | biostudies-literature

Enantioselective Synthesis of Five-Membered-Ring Atropisomers with a Chiral Rh(III) Complex.

Project description:Axially chiral atropisomeric compounds are widely applied in asymmetric catalysis and medicinal chemistry, and efficient methods for their synthesis are in high demand. This applies in particular to atropisomers derived from five-membered aromatic rings because their lower barrier for rotation among the biaryl axis limits their asymmetric synthesis. We report here an enantioselective C-H functionalization method using our chiral RhJasCp complex for the synthesis of the biaryl atropisomer types that can be accessed from three different five-membered-ring heterocycles.

| S-EPMC7735750 | biostudies-literature

Efficient Access to Chiral Trisubstituted Aziridines via Catalytic Enantioselective Aza-Darzens Reactions.

Project description:Herein, we report a Zn-ProPhenol catalyzed aza-Darzens reaction using chlorinated aromatic ketones as nucleophilic partners for the efficient and enantioselective construction of complex trisubstituted aziridines. The ?-chloro-?-aminoketone intermediates featuring a chlorinated tetrasubstituted stereocenter can be isolated in high yields and selectivities for further derivatization. Alternatively, they can be directly transformed to the corresponding aziridines in a one-pot fashion. Of note, the reaction can be run on gram-scale with low catalyst loading without impacting its efficiency. Moreover, this methodology was extended to ?-bromoketones which are scarcely used in enantioselective catalysis because of their sensitivity and lack of accessibility.

| S-EPMC5530870 | biostudies-literature

Stereoselective synthesis of isoquinuclidines through an aza-[4 + 2] cycloaddition of chiral cyclic 2-amidodienes.

Project description:A highly stereoselective aza-[4 + 2] cycloaddition of chiral cyclic 2-amidodienes with N-sulfonyl aldimines is described. While this Lewis acid promoted heterocycloaddition provides an efficient strategy for constructing optically enriched isoquinuclidines, it is mechanistically intriguing. The cycloaddition favored the endo-II pathway in the absence of a viable bidentate coordination. This represents an unexpected switch from the anticipated endo-I selectivity obtained in the all-carbon cycloaddition.

| S-EPMC3969095 | biostudies-literature

Photoinduced Carboborative Ring Contraction Enables Regio- and Stereoselective Synthesis of Multiply Substituted Five-Membered Carbocycles and Heterocycles.

Project description:We report herein a photoinduced carboborative ring contraction of monounsaturated six-membered carbocycles and heterocycles. The reaction produces substituted five-membered ring systems stereoselectively and on preparative scales. The products feature multiple stereocenters, including contiguous quaternary carbons. We show that the reaction can serve as a synthetic platform for ring system alteration of natural products. The reaction can also be used in natural product synthesis. A concise total synthesis of artalbic acid has been enabled by a sequence of photoinduced carboborative ring contraction, Rauhut-Currier reaction, and nitrilase-catalyzed hydrolysis. The synthetic utility of the reaction has been further demonstrated by converting the intermediate organoboranes to alcohols, amines, and alkenes.

| S-EPMC5737778 | biostudies-literature

Mechanistic Studies of Cobalt-Catalyzed C(sp2)-H Borylation of Five-Membered Heteroarenes with Pinacolborane.

Project description:Studies into the mechanism of cobalt-catalyzed C(sp2)-H borylation of five-membered heteroarenes with pinacolborane (HBPin) as the boron source established the catalyst resting state as the trans-cobalt(III) dihydride boryl, (iPrPNP)Co(H)2(BPin) (iPrPNP = 2,6-(iPr2PCH2)2(C5H3N)), at both low and high substrate conversions. The overall first-order rate law and observation of a normal deuterium kinetic isotope effect on the borylation of benzofuran versus benzofuran-2-d1 support H2 reductive elimination from the cobalt(III) dihydride boryl as the turnover-limiting step. These findings stand in contrast to that established previously for the borylation of 2,6-lutidine with the same cobalt precatalyst, where borylation of the 4-position of the pincer occurred faster than the substrate turnover and arene C-H activation by a cobalt(I) boryl is turnover-limiting. Evaluation of the catalytic activity of different cobalt precursors in the C-H borylation of benzofuran with HBPin established that the ligand design principles for C- H borylation depend on the identities of both the arene and the boron reagent used: electron-donating groups improve catalytic activity of the borylation of pyridines and arenes with B2Pin2, whereas electron-withdrawing groups improve catalytic activity of the borylation of five-membered heteroarenes with HBPin. Catalyst deactivation by P-C bond cleavage from a cobalt(I) hydride was observed in the C-H borylation of arene substrates with C-H bonds that are less acidic than those of five-membered heteroarenes using HBPin and explains the requirement of B2Pin2 to achieve synthetically useful yields with these arene substrates.

| S-EPMC5822728 | 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