Browse
Submit Data
Databases
API
Help

Dataset Information

31 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Chemospecific Cyclizations of ?-Carbonyl Sulfoxonium Ylides on Aryls and Heteroaryls.

ABSTRACT: The functionalization of aryl and heteroaryls using ?-carbonyl sulfoxonium ylides without the help of a directing group has remained so far a neglected area, despite the advantageous safety profile of sulfoxonium ylides. Described herein are the cyclizations of ?-carbonyl sulfoxonium ylides onto benzenes, benzofurans and N-p-toluenesulfonyl indoles in the presence of a base in HFIP, whereas pyrroles and N-methyl indoles undergo cyclization in the presence of an iridium catalyst. Significantly, these two sets of conditions are chemospecific for each groups of substrates.

SUBMITTER: Clare D

PROVIDER: S-EPMC6856693 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Chemospecific Cyclizations of α-Carbonyl Sulfoxonium Ylides on Aryls and Heteroaryls.

Clare Daniel D Dobson Benjamin C BC Inglesby Phillip A PA Aïssa Christophe C

Angewandte Chemie (International ed. in English) 20190924 45

The functionalization of aryl and heteroaryls using α-carbonyl sulfoxonium ylides without the help of a directing group has remained so far a neglected area, despite the advantageous safety profile of sulfoxonium ylides. Described herein are the cyclizations of α-carbonyl sulfoxonium ylides onto benzenes, benzofurans and N-p-toluenesulfonyl indoles in the presence of a base in HFIP, whereas pyrroles and N-methyl indoles undergo cyclization in the presence of an iridium catalyst. Significantly, t ...[more]

PMID: 31507055

Similar Datasets

Enantioselective S-H Insertion Reactions of α-Carbonyl Sulfoxonium Ylides.

Project description:The first example of enantioselective S-H insertion reactions of sulfoxonium ylides is reported. Under the influence of thiourea catalysis, excellent levels of enantiocontrol (up to 95 % ee) and yields (up to 97 %) are achieved for 31 examples in S-H insertion reactions of aryl thiols and α-carbonyl sulfoxonium ylides.

| S-EPMC7606806 | biostudies-literature

Ruthenium(II)-Catalyzed Homocoupling of α-Carbonyl Sulfoxonium Ylides Under Mild Conditions: Methodology Development and Mechanistic DFT Study.

Project description:A mild ruthenium(II)-catalyzed homocoupling of α-carbonyl sulfoxonium ylides was developed and the detailed mechanism was understood based on DFT calculations in the current report. The catalytic system utilizes the α-carbonyl sulfoxonium ylide as both the directing group for ortho-sp2 C-H activation and the acylmethylating reagent for C-C coupling. Various substituents are compatible in the transformation and a variety of isocoumarin derivatives were synthesized at room temperature without any protection. The theoretical results disclosed that the full catalytic cycle contains eight elementary steps, and in all the cationic Ru(II) monomer is involved as the catalytic active species. The acid additive is responsible for protonation of the ylide carbon prior to the intramolecular nucleophilic addition and C-C bond cleavage. Interestingly, the intermediacy of free acylmethylation intermediate or its enol isomer is not necessary for the transformation.

| S-EPMC7525066 | biostudies-literature

Insights into the Activation Mode of α-Carbonyl Sulfoxonium Ylides in Rhodium-Catalyzed C-H Activation: A Theoretical Study.

Project description:A computational study has been performed to investigate the mechanism of RhIII -catalyzed C-H bond activation using sulfoxonium ylides as a carbene precursor. The stepwise and concerted activation modes for sulfoxonium ylides were investigated. Detailed theoretical results showed that the favored stepwise pathway involves C-H bond activation, carbonization, carbene insertion, and protonation. The free energy profiles for dialkylation of 2-phenylpyridine were also calculated to account for the low yield of this reaction. Furthermore, the substituent effect was elucidated by comparing the energy barriers for the protonation of meta- and para-substituted sulfoxonium ylides calculated by density functional theory.

| S-EPMC9278107 | biostudies-literature

Organocatalytic asymmetric synthesis of α-amino esters from sulfoxonium ylides.

Project description:Described here is the first organocatalytic asymmetric N-H insertion reaction of α-carbonyl sulfoxonium ylides. Without a metal catalyst, this reaction represents an attractive complement to the well-established carbene insertion reactions. As a stable surrogate of diazocarbonyl compounds, sulfoxonium ylides reacted with a range of aryl amines to provide efficient access to α-aryl glycines with excellent enantiocontrol in the presence of a suitable chiral phosphoric acid catalyst. The high stability and weak basicity of sulfoxonium ylides not only enable this protocol to be user-friendly and practically useful, but also preclude catalyst decomposition, which is crucial to the excellent amenability to electron-poor amine nucleophiles. Detailed mechanistic studies indicated that the initial protonation is reversible and the C-N bond formation is rate-determining.

| S-EPMC8386753 | biostudies-literature

A Catalytic Cross-Olefination of Diazo Compounds with Sulfoxonium Ylides.

Project description:A ruthenium-catalysed cross-olefination of diazo compounds and sulfoxonium ylides is presented. Our reaction design exploits the intrinsic difference in reactivity of diazo compounds and sulfoxonium ylides as both carbene precursors and nucleophiles, which results in a highly selective reaction.

| S-EPMC6283242 | biostudies-other

Sulfoxonium Ylides in Aminocatalysis: An Enantioselective Entry to Cyclopropane-Fused Chromanol Structures.

Project description:The 1,1a,2,7b-tetrahydrocyclopropa[c]chromene, arising from fusion of chromane and cyclopropane rings is the core of medicinally relevant compounds. Engaging sulfoxonium ylides in enantioselective aminocatalytic reactions for the first time, a convenient entry to this scaffold is presented. Several ring-fused derivatives were obtained in moderate-to-good yields and enantioselectivities and with perfect diastereoselectivity at the cyclopropane, using an α,α-diphenylprolinol aminocatalyst. The versatility of the hemiacetal moiety in the products was leveraged to effect various synthetic manipulations.

| S-EPMC9344464 | biostudies-literature

Cooperative copper-squaramide catalysis for the enantioselective N-H insertion reaction with sulfoxonium ylides.

Project description:The first examples of a highly efficient and enantioselective carbene-mediated insertion reaction, from a sulfur ylide, are described. By way of a catalytic asymmetric insertion reaction into N-H bonds from carbonyl sulfoxonium ylides and anilines, using a copper-bifunctional squaramide cooperative catalysis approach, thirty-seven α-arylglycine esters were synthesized in enantiomeric ratios up to 92 : 8 (99 : 1 after a single recrystallization) and reaction yields ranging between 49-96%. Furthermore, the protocol benefits from quick reaction times and is conducted in a straightforward manner.

| S-EPMC8171336 | biostudies-literature

Terpolymers from Borane-Initiated Copolymerization of Triphenyl Arsonium and Sulfoxonium Ylides: An Unexpected Light Emission.

Project description:The first synthesis of well-defined poly[(phenylmethylene-co-methylpropenylene)-b-methylene, [(C1-co-C3)-b-C1], terpolymers was achieved by one-pot borane-initiated random copolymerization of ω-methylallyl (C3 units, chain is growing by three carbon atoms at a time) and benzyltriphenylarsonium (C1 units, chain is growing by one carbon atom at a time) ylides, followed by polymerization of sulfoxonium methylide (C1 units). Other substituted arsonium ylides, such as prenyltriphenyl, propyltriphenyl and (4-fluorobenzyl)triphenyl can also be used instead of benzyltriphenylarsonium. The obtained terpolymers are well-defined, possess a predictable molecular weight and low polydispersity (Mn,NMR =1.83-9.68×103 g mol-1 , Đ=1.09-1.22). An unexpected light emission phenomenon was discovered in these non-conjugated terpolymers, as confirmed by fluorescence and NMR spectroscopy. This phenomenon can be explained by the isomerization of the double bonds of allylic monomeric units along the chain of the terpolymers (isomerization-induced light emission).

| S-EPMC6593832 | biostudies-literature

Direct Stereodivergent Olefination of Carbonyl Compounds with Sulfur Ylides.

Project description:The reactivity of phosphorus and sulfur ylides toward carbonyl compounds constitutes a well-known dichotomy that is a common educational device in organic chemistry─the former gives olefins, while the latter gives epoxides. Herein, we report a stereodivergent carbonyl olefination that challenges this dichotomy, showcasing thiouronium ylides as valuable olefination reagents. With this method, aldehydes are converted to Z-alkenes with high stereoselectivity and broad substrate scope, while N-tosylimines provide a similarly proficient entry to E-alkenes. In-depth computational and experimental studies clarified the mechanistic details of this unusual reactivity.

| S-EPMC9284548 | biostudies-literature

Ru(ii)-catalyzed C6-selective C-H acylmethylation of pyridones using sulfoxonium ylides as carbene precursors.

Project description:In this study, we describe a method using sulfoxonium ylides as carbene precursors to achieve C6-selective acylmethylation of pyridones catalyzed by a ruthenium(ii) complex. This approach featured mild reaction conditions, moderate to excellent yields, high step economy, and had excellent functional group tolerance with good site selectivity. Besides, gram-scale preparation, synthetic utility, and mechanistic studies were conducted. It offers a direct and efficient way to synthesize pyridone derivatives.

| S-EPMC9049633 | 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