Browse
Submit Data
Databases
API
Help

Dataset Information

23 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Rh-Catalyzed Highly Enantioselective Synthesis of Aliphatic Sulfonyl Fluorides.

ABSTRACT: Rh-catalyzed, highly enantioselective (up to 99.8% ee) synthesis of aliphatic sulfonyl fluorides was accomplished. This protocol provides a portal to a class of novel 2-aryl substituted chiral sulfonyl fluorides, which are otherwise extremely difficult to access. This asymmetric synthesis has the feature of mild conditions, excellent functional group compatibility, and wide substrate scope (51 examples) generating a wide array of structurally unique chiral ?-arylated sulfonyl fluorides for sulfur(VI) fluoride exchange (SuFEx) click reaction and drug discovery.

SUBMITTER: Moku B

PROVIDER: S-EPMC6889689 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

A rapid access to aliphatic sulfonyl fluorides.

Project description:The past few years have witnessed a fast-growing research interest on the study of sulfonyl fluorides as reactive probes in chemical biology and molecular pharmacology, which raises an urgent need for the development of effective synthetic methods to expand the toolkit. Herein, we present the invention of a facile and general approach for the synthesis of aliphatic sulfonyl fluorides via visible-light-mediated decarboxylative fluorosulfonylethylation. The method is based on abundant carboxylic acid feed stock, applicable to various alkyl carboxylic acids including primary, secondary, and tertiary acids, and is also suitable for the modification of natural products like amino acids, peptides, as well as drugs, forging a rapid, metal-free approach to build sulfonyl fluoride compound libraries of considerable structural diversity. Further diversification of the SO2F-containing products is also demonstrated, which allows for access to a range of pharmaceutically important motifs such as sultam, sulfonate, and sulfonamide.

| S-EPMC6704106 | biostudies-literature

One-pot palladium-catalyzed synthesis of sulfonyl fluorides from aryl bromides.

Project description:A mild, efficient synthesis of sulfonyl fluorides from aryl and heteroaryl bromides utilizing palladium catalysis is described. The process involves the initial palladium-catalyzed sulfonylation of aryl bromides using DABSO as an SO2 source, followed by in situ treatment of the resultant sulfinate with the electrophilic fluorine source NFSI. This sequence represents the first general method for the sulfonylation of aryl bromides, and offers a practical, one-pot alternative to previously described syntheses of sulfonyl fluorides, allowing rapid access to these biologically important molecules. Excellent functional group tolerance is demonstrated, with the transformation successfully achieved on a number of active pharmaceutical ingredients, and their precursors. The preparation of peptide-derived sulfonyl fluorides is also demonstrated.

| S-EPMC5369543 | biostudies-literature

Enantioselective synthesis of cyclobutanes via sequential Rh-catalyzed bicyclobutanation/Cu-catalyzed homoconjugate addition.

Project description:Enantiomerically enriched cyclobutanes are constructed by a three-component process in which t-butyl (E)-2-diazo-5-arylpent-4-enoates are treated with Rh2(S-NTTL)4 to provide enantiomerically enriched bicyclobutanes, which can subsequently engage in homoconjugate addition/enolate trapping sequence to give densely functionalized cyclobutanes with high diastereoselectivity. This three-component, two-catalyst procedure can be carried out in a single flask. Rh2(S-NTTL)4-catalyzed reaction of t-butyl (Z)-2-diazo-5-phenylpent-4-enoate gives the Büchner cyclization product in excellent enantioselectivity.

| S-EPMC3908885 | biostudies-literature

Facile synthesis of sulfonyl fluorides from sulfonic acids.

Project description:Herein, we demonstrate two complementary strategies for the syntheses of sulfonyl fluorides using sulfonic acids and their salts. One strategy involves the conversion of sulfonic acid sodium salts to sulfonyl fluorides using thionyl fluoride in 90-99% yields in one hour. Lessons learned from the mechanism of this reaction also have enabled a complementary deoxyfluorination of sulfonic acids using Xtalfluor-E® - a bench stable solid - allowing for the conversion of both aryl and alkyl sulfonic acids and salts to sulfonyl fluorides in 41-94% yields. Notably, using Xtalfluor-E® enabled milder conditions and the use of both sulfonic acids and their sodium salts.

| S-EPMC9835472 | biostudies-literature

Highly Enantioselective Hiyama Cross-Coupling via Rh-Catalyzed Allylic Arylation of Racemic Allyl Chlorides.

Project description:Highly enantioselective Hiyama cross-coupling reactions have been achieved through rhodium(I)-catalyzed dynamic kinetic asymmetric transformations between aryl siloxanes and cyclic racemic allyl halides. This process affords valuable enantiomerically enriched aryl-substituted cyclic allyl products and is compatible with heterocyclic allyl chloride electrophiles.

| S-EPMC7009026 | biostudies-literature

Copper-Promoted Conjugate Addition of Carboxylic Acids to Ethenesulfonyl Fluoride (ESF) for Constructing Aliphatic Sulfonyl Fluorides.

Project description:A CuO-promoted direct hydrocarboxylation of ethenesulfonyl fluoride (ESF) was developed using carboxylic acid as a nucleophile under mild conditions. A variety of molecules containing both ester group and aliphatic sulfonyl fluoride moiety exhibit great potential in medicinal chemistry and chemical biology. Furthermore, the modification of the known drugs Ibuprofen and Aspirin was also demonstrated.

| S-EPMC8515394 | biostudies-literature

Enantioselective formal synthesis of (-)-englerin A via a Rh-catalyzed [4 + 3] cycloaddition reaction.

Project description:An enantioselective formal synthesis of (-)-englerin A (1) is reported. Key to the strategy is a Rh-catalyzed [4 + 3] cycloaddition reaction between furan 10 and diazo ester 11 that, following an intramolecular aldol condensation, produces the tricyclic scaffold of englerin. This strategy also provides a rapid, efficient, and stereoselective access to the biologically significant core motif of the guaiane sesquiterpenes.

| S-EPMC2927118 | biostudies-literature

Highly Enantioselective Oxidation of Nonactivated Aliphatic C-H Bonds with Hydrogen Peroxide Catalyzed by Manganese Complexes.

Project description:Monosubstituted cycloalkanes undergo regio- and enantioselective aliphatic C-H oxidation with H2O2 catalyzed by biologically inspired manganese catalysts. The reaction furnishes the corresponding ketones resulting from oxidation at C3 and C4 methylenic sites (K3 and K4, respectively) leading to a chiral desymmetrization that proceeds with remarkable enantioselectivity (64% ee) but modest regioselectivity at C3 (K3/K4 ≈ 2) for tert-butylcyclohexane, and with up to 96% ee and exquisite regioselectity toward C3 (up to K3/K4 > 99) when N-cyclohexylalkanamides are employed as substrates. Efficient H2O2 activation, high yield, and highly enantioselective C-H oxidation rely on the synergistic cooperation of a sterically bulky manganese catalyst and an oxidatively robust alkanoic acid. This represents the first example of nonenzymatic highly enantioselective oxidation of nonactivated methylenic sites. Furthermore, the principles of catalyst design disclosed in this work constitute a unique platform for further development of stereoselective C-H oxidation reactions.

| S-EPMC5364455 | biostudies-literature

Enantioselective nucleophile-catalyzed synthesis of tertiary alkyl fluorides via the ?-fluorination of ketenes: synthetic and mechanistic studies.

Project description:The catalytic asymmetric synthesis of alkyl fluorides, particularly ?-fluorocarbonyl compounds, has been the focus of substantial effort in recent years. While significant progress has been described in the formation of enantioenriched secondary alkyl fluorides, advances in the generation of tertiary alkyl fluorides have been more limited. Here, we describe a method for the catalytic asymmetric coupling of aryl alkyl ketenes with commercially available N-fluorodibenzenesulfonimide (NFSI) and C6F5ONa to furnish tertiary ?-fluoroesters. Mechanistic studies are consistent with the hypothesis that the addition of an external nucleophile (C6F5ONa) is critical for turnover, releasing the catalyst (PPY*) from an N-acylated intermediate. The available data can be explained by a reaction pathway wherein the enantioselectivity is determined in the turnover-limiting transfer of fluorine from NFSI to a chiral enolate derived from the addition of PPY* to the ketene. The structure and the reactivity of the product of this proposed elementary step, an ?-fluoro-N-acylpyridinium salt, have been examined.

| S-EPMC4091276 | biostudies-literature

Highly diastereo- and enantioselective CuH-catalyzed synthesis of 2,3-disubstituted indolines.

Project description:A diastereo- and enantioselective CuH-catalyzed method for the preparation of highly functionalized indolines is reported. The mild reaction conditions and high degree of functional group compatibility as demonstrated with substrates bearing heterocycles, olefins, and substituted aromatic groups, renders this technique highly valuable for the synthesis of a variety of cis-2,3-disubstituted indolines in high yield and enantioeselectivity.

| S-EPMC4440622 | 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