Browse
Submit Data
Databases
API
Help

Dataset Information

14 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Regio- and Stereoselective Thianthrenation of Olefins To Access Versatile Alkenyl Electrophiles.

ABSTRACT: Herein, we report a regioselective alkenyl electrophile synthesis from unactivated olefins that is based on a direct and regioselective C-H thianthrenation reaction. The selectivity is proposed to arise from an unusual inverse-electron-demand hetero-Diels-Alder reaction. The alkenyl sulfonium salts can serve as electrophiles in palladium- and ruthenium-catalyzed cross-coupling reactions to make alkenyl C-C, C-Cl, C-Br, and C-SCF3 bonds with stereoretention.

SUBMITTER: Chen J

PROVIDER: S-EPMC7154751 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Regio- and Stereoselective Thianthrenation of Olefins To Access Versatile Alkenyl Electrophiles.

Chen Junting J Li Jiakun J Plutschack Matthew B MB Berger Florian F Ritter Tobias T

Angewandte Chemie (International ed. in English) 20200203 14

Herein, we report a regioselective alkenyl electrophile synthesis from unactivated olefins that is based on a direct and regioselective C-H thianthrenation reaction. The selectivity is proposed to arise from an unusual inverse-electron-demand hetero-Diels-Alder reaction. The alkenyl sulfonium salts can serve as electrophiles in palladium- and ruthenium-catalyzed cross-coupling reactions to make alkenyl C-C, C-Cl, C-Br, and C-SCF<sub>3</sub> bonds with stereoretention. ...[more]

PMID: 31782968

Similar Datasets

Efficient regio- and stereoselective access to novel fluorinated ?-aminocyclohexanecarboxylates.

Project description:A regio- and stereoselective method has been developed for the synthesis of novel fluorinated 2-aminocyclohexanecarboxylic acid derivatives with the fluorine attached to position 4 of the ring. The synthesis starts from either cis- or trans-?-aminocyclohex-4-enecarboxylic acids and involves regio- and stereoselective transformation of the ring C-C double bond through iodooxazine formation and hydroxylation, followed by hydroxy-fluorine or oxo-fluorine exchange.

| S-EPMC3701410 | biostudies-literature

Direct Access to Versatile Electrophiles via Catalytic Oxidative Cyanation of Alkenes.

Project description:Nucleophilic attack on carbon-based electrophiles is a central reactivity paradigm in chemistry and biology. The steric and electronic properties of the electrophile dictate its reactivity with different nucleophiles of interest, allowing the opportunity to fine-tune electrophiles for use as coupling partners in multistep organic synthesis or for covalent modification of proteins in drug discovery. Reactions that directly transform inexpensive chemical feedstocks into versatile carbon electrophiles would therefore be highly enabling. Herein, we report the catalytic, regioselective oxidative cyanation of conjugated and nonconjugated alkenes using a homogeneous copper catalyst and a bystanding N-F oxidant to furnish branched alkenyl nitriles that are difficult to prepare using existing methods. We show that the alkenyl nitrile products serve as electrophilic reaction partners for both organic synthesis and the chemical proteomic discovery of covalent protein ligands.

| S-EPMC6033665 | biostudies-literature

Regio- and Enantioselective (Het)arylation of β-Alkenyl Pyrroline to α-Aryl-β-alkenyl Pyrrolidines.

Project description:Regio- and enantioselective direct arylation of β-alkenyl pyrroline is reported. A wide range of electron-rich arenes and heteroarenes reacted under mild conditions with different β-alkenyl pyrrolines to provide structurally diverse α-aryl-β-alkenyl pyrrolidines with very good yields and excellent regioselectivity. Enantioselective reaction in the presence of Lewis acids and chiral phosphoric acids provided the desired arylated product with 73% enantiomeric excess.

| S-EPMC6649053 | biostudies-literature

Regio- and stereoselective synthesis of new diaminocyclopentanols.

Project description:The optimal conditions for regio- and stereoselective epoxide ring opening of N,N-disubstituted 1,2-epoxy-3-aminocyclopentanes by different nucleophilic reagents have been developed. The substituents on the nitrogen atom in the epoxide precursor and the orientation of the oxirane ring are crucial for the reaction outcome. Thus, treatment of (1RS,2SR,3SR)-1,2-epoxy-3-(N,N-dibenzylamino)cyclopentane (3b) with amines gave a mixture of C1 and C2 regioadducts, while the use of (1RS,2SR,3SR)-1,2-epoxy-3-(N-benzyl-N-methylamino)cyclopentane (3a) led ultimately to C1 adducts. Base-catalyzed aminolysis of epoxides 6a,b afforded mainly C1 adducts 13a,b arising from trans-diaxal opening of the epoxide ring. Using a Lewis acid catalyst, epoxides 6a,b were transformed into diaminocyclopentanols 14a,b via an alternative pathway involving the formation of aziridinium intermediate 17.

| S-EPMC4222406 | biostudies-literature

Catalytic enantioconvergent coupling of secondary and tertiary electrophiles with olefins.

Project description:Carbon-carbon bonds, including those between sp3-hybridized carbon atoms (alkyl-alkyl bonds), typically comprise much of the framework of organic molecules. In the case of sp3-hybridized carbon, the carbon can be stereogenic and the particular stereochemistry can have implications for structure and function1-3. As a consequence, the development of methods that simultaneously construct alkyl-alkyl bonds and control stereochemistry is important, although challenging. Here we describe a strategy for enantioselective alkyl-alkyl bond formation, in which a racemic alkyl electrophile is coupled with an olefin in the presence of a hydrosilane, rather than via a traditional electrophile-nucleophile cross-coupling, through the action of a chiral nickel catalyst. We demonstrate that families of racemic alkyl halides-including secondary and tertiary electrophiles, which have not previously been shown to be suitable for enantioconvergent coupling with alkyl metal nucleophiles-cross-couple with olefins with good enantioselectivity and yield under very mild reaction conditions. Given the ready availability of olefins, our approach opens the door to developing more general methods for enantioconvergent alkyl-alkyl coupling.

| S-EPMC6296363 | biostudies-literature

Iridium-Catalyzed Regio- and Enantioselective Allylic Substitution of Trisubstituted Allylic Electrophiles.

Project description:The first Ir-catalyzed enantioselective allylation of trisubstituted allylic electrophiles has been developed. Through modification of the leaving group of allylic electrophiles, we found that trisubstituted allylic phosphates are suitable electrophiles for asymmetric allylation. The reaction of allylic phosphates with enol silanes derived from dioxinones gave allylated products in good yields with high enantioselectivities.

| S-EPMC5213737 | biostudies-literature

Regio- and stereoselective Ni-catalyzed 1,4-hydroboration of 1,3-dienes: access to stereodefined (Z)-allylboron reagents and derived allylic alcohols.

Project description:A catalytic regio- and stereoselective 1,4-hydroboration of 1,3-dienes was accomplished with pinacolborane in the presence of Ni(cod)(2) and PCy(3). This reaction exhibits broad substrate scope operating on a range of substituted dienes and occurs with generally high levels of selectivity and efficiency. Reactivity patterns suggest that the reactive conformation of the diene is the S-cis form. The intermediate allylboronate can be oxidized to stereodefined allylic alcohols or can be used in stereoselective carbonyl addition reactions.

| S-EPMC2858638 | biostudies-literature

Olefin-Directed Palladium-Catalyzed Regio- and Stereoselective Oxidative Arylation of Allenes.

Project description:An olefin-directed palladium-catalyzed oxidative regio- and stereoselective arylation of allenes to afford 1,3,6-trienes has been established. A number of functionalized allenes, including 2,3- and 3,4-dienoates and 3,4-dienol derivatives, have been investigated and found to undergo the olefin-directed allene arylation. The olefin moiety has been proven to be a crucial element for the arylating transformation.

| S-EPMC4832836 | biostudies-other

Regio- and stereoselective carbometallation reactions of N-alkynylamides and sulfonamides.

Project description:The carbocupration reactions of heterosubstituted alkynes allow the regio- and stereoselective formation of vinyl organometallic species. N-Alkynylamides (ynamides) are particularly useful substrates for the highly regioselective carbocupration reaction, as they lead to the stereodefined formation of vinylcopper species geminated to the amide moiety. The latter species are involved in numerous synthetically useful transformations leading to valuable building blocks in organic synthesis. Here we describe in full the results of our studies related to the carbometallation reactions of N-alkynylamides.

| S-EPMC3628878 | biostudies-literature

Integrated redox-active reagents for photoinduced regio- and stereoselective fluorocarboborylation.

Project description:Vinylboronates and alkylboronates are key components in variegated transformations in all facets of chemical science. The synthesis of vinylboronates and alkylboronates suffers from step-tedious and poor stereoselective procedures. We have developed a regulated radical difunctionalization strategy for the construction of fluorine-containing vinylboronates and alkylboronates with an integrated redox-active reagent IMDN-SO2RF. This bench-stable imidazolium sulfonate cationic salt offers a scalable and operational protocol for the fluoroalkylation-borylation of unsaturated hydrocarbons in a high regio- and stereoselective manner. The products can be further transformed into valuable fluorinated building blocks.

| S-EPMC7244735 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

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