Browse
Submit Data
Databases
API
Help

Dataset Information

45 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Chiral Hypervalent Iodine Catalysis Enables an Unusual Regiodivergent Intermolecular Olefin Aminooxygenation.

ABSTRACT: A novel iodide-catalyzed intermolecular aminooxygenation strategy is described here. Amide is used as the O- and N- source to probe for regiocontrol strategies. Notably, simple additives can be selectively introduced to achieve regiodivergent oxyamination processes for electronically activated alkenes while being regio-complementary for unactivated alkenes. Our preliminary data demonstrates that this regiocontrol strategy based on nucleophile can also be applied in asymmetric processes using chiral hypervalent iodine catalysis.

SUBMITTER: Wu F

PROVIDER: S-EPMC8243328 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Chiral Hypervalent Iodine Catalysis Enables an Unusual Regiodivergent Intermolecular Olefin Aminooxygenation.

Wu Fan F Kaur Navdeep N Alom Nur-E NE Li Wei W

JACS Au 20210429 6

A novel iodide-catalyzed intermolecular aminooxygenation strategy is described here. Amide is used as the O- and N- source to probe for regiocontrol strategies. Notably, simple additives can be selectively introduced to achieve regiodivergent oxyamination processes for electronically activated alkenes while being regio-complementary for unactivated alkenes. Our preliminary data demonstrates that this regiocontrol strategy based on nucleophile can also be applied in asymmetric processes using chi ...[more]

PMID: 34240078

Similar Datasets

Enantioselective Oxidative Rearrangements with Chiral Hypervalent Iodine Reagents.

Project description:A stereoselective hypervalent iodine-promoted oxidative rearrangement of 1,1-disubstituted alkenes has been developed. This practically simple protocol provides access to enantioenriched α-arylated ketones without the use of transition metals from readily accessible alkenes.

| S-EPMC4797713 | biostudies-literature

Enantioselective diamination with novel chiral hypervalent iodine catalysts.

Project description:Vicinal diamines constitute one the most important functional motif in organic chemistry because of its wide occurrence in a variety of biological and pharmaceutical molecules. We report an efficient metal-free, highly stereoselective intramolecular diamination using a novel chiral hypervalent iodine reagent together with its application as an efficient catalyst for the synthesis of diamines.

| S-EPMC4736455 | biostudies-literature

Structurally Defined Molecular Hypervalent Iodine Catalysts for Intermolecular Enantioselective Reactions.

Project description:Molecular structures of the most prominent chiral non-racemic hypervalent iodine(III) reagents to date have been elucidated for the first time. The formation of a chirally induced supramolecular scaffold based on a selective hydrogen-bonding arrangement provides an explanation for the consistently high asymmetric induction with these reagents. As an exploratory example, their scope as chiral catalysts was extended to the enantioselective dioxygenation of alkenes. A series of terminal styrenes are converted into the corresponding vicinal diacetoxylation products under mild conditions and provide the proof of principle for a truly intermolecular asymmetric alkene oxidation under iodine(I/III) catalysis.

| S-EPMC4832830 | biostudies-literature

Regiodivergent Electrophotocatalytic Aminooxygenation of Aryl Olefins.

Project description:A method for the regiodivergent aminooxygenation of aryl olefins under electrophotocatalytic conditions is described. The procedure employs a trisaminocyclopropenium (TAC) ion catalyst with visible light irradiation under a controlled electrochemical potential to convert aryl olefins to the corresponding oxazolines with high chemo- and diastereoselectivity. With the judicious choice between two inexpensive and abundant reagents, namely water and urethane, either 2-amino-1-ol or 1-amino-2-ol derivatives could be prepared from the same substrate. This method is amenable to multigram synthesis of the oxazoline products with low catalyst loadings.

| S-EPMC10405276 | biostudies-literature

Enantioselective dioxytosylation of styrenes using lactate-based chiral hypervalent iodine(III).

Project description:A series of optically active hypervalent iodine(III) reagents prepared from the corresponding (R)-2-(2-iodophenoxy)propanoate derivative was employed for the asymmetric dioxytosylation of styrene and its derivatives. The electrophilic addition of the hypervalent iodine(III) compound toward styrene proceeded with high enantioface selectivity to give 1-aryl-1,2-di(tosyloxy)ethane with an enantiomeric excess of 70-96% of the (S)-isomer.

| S-EPMC5870148 | biostudies-literature

Regio- and Enantioselective Intermolecular Aminofluorination of Alkenes via Iodine(I)/Iodine(III) Catalysis.

Project description:The regio- and enantio-selective, intermolecular vicinal fluoroamination of α-trifluoromethyl styrenes has been achieved by enantioselective II /IIII catalysis. Leveraging C2 -symmetric resorcinol-based aryl iodide catalysts, it has been possible to intercept the transient iodonium intermediate using simple nitriles, which function as both the solvent and nucleophile. In situ Ritter reaction provides direct access to the corresponding amides (up to 89 % yield, e.r. 93 : 7). This main group catalysis paradigm inverts the intrinsic regioselectivity of the uncatalyzed process, thereby providing facile access to tertiary, benzylic stereocenters bearing both CF3 and F groups. Privileged phenethylamine pharmacophores can be generated in which there is complete local partial charge inversion (CF3 δ- /Fδ- versus CH3 δ+ /Hδ+ ). Crystallographic analyses of representative β-fluoroamide products reveal highly pre-organized conformations that manifest the stereoelectronic gauche effect.

| S-EPMC9400885 | biostudies-literature

C-N Axial Chiral Hypervalent Iodine Reagents: Catalytic Stereoselective α-Oxytosylation of Ketones.

Project description:A simple synthesis of a library of novel C-N axially chiral iodoarenes is achieved in a three-step synthesis from commercially available aniline derivatives. C-N axial chiral iodine reagents are rarely investigated in the hypervalent iodine arena. The potential of the novel chiral iodoarenes as organocatalysts for stereoselective oxidative transformations is assessed using the well explored, but challenging stereoselective α-oxytosylation of ketones. All investigated reagents catalyse the stereoselective oxidation of propiophenone to the corresponding chiral α-oxytosylated products with good stereochemical control. Using the optimised reaction conditions a wide range of products was obtained in generally good to excellent yields and with good enantioselectivities.

| S-EPMC7986903 | biostudies-literature

Chiral Hypervalent, Pentacoordinated Phosphoranes.

Project description:This review presents synthetic procedures applied to the preparation of chiral (mainly optically active) pentacoordinated, hypervalent mono and bicyclic phosphoranes. The mechanisms of their stereoisomerization and their selected interconversions are also presented.

| S-EPMC6274329 | biostudies-other

Hypervalent iodine(III)-promoted intermolecular C-C coupling of vindoline with β-ketoesters and related substrates.

Project description:The regioselective intermolecular coupling reaction of vindoline with a wide range of substrates including β-ketoesters, β-diketones, β-ketoaldehydes, β-ketonitriles, malononitriles, and β-cyanoesters provides an opportunity for the synthesis of vinblastine analogues containing deep-seated changes in the upper velbanamine subunit. The transition-metal-free hypervalent iodine(III)-promoted intermolecular sp(3)/sp(2) coupling, representing a special class of selective C-H activation with direct carbon-carbon bond formation, proceeds with generation of a quaternary center capable of incorporation of the vinblastine C16' methyl ester and functionalized for subsequent divergent heterocycle introduction.

| S-EPMC3607625 | biostudies-literature

Structure Elucidation of In Situ Generated Chiral Hypervalent Iodine Complexes via Vibrational Circular Dichroism (VCD).

Project description:The structure of in situ generated chiral aryl-λ3 -iodanes obtained under oxidative reaction conditions was not yet observable with experimental techniques and their proposed structures are purely based on DFT calculations. Herein, we establish vibrational circular dichroism (VCD) spectroscopy as an experimental technique to verify DFT-calculated chiral iodane structures. Based on a chiral triazole-substituted iodoarene catalyst, we were able to elucidate a yet undescribed cationic chiral iodane as the most populated intermediate under oxidative conditions with a significant intramolecular N-I-interaction and no significant interactions with tosylate or m-chlorobenzoic acid as potential anionic ligands. Instead, aggregation of these substrates was found, which resulted in the formation of a non-coordinating anionic hydrogen bonded complex. The importance of VCD as a crucial experimental observable is further highlighted by the fact that our initial structural proposal, that was purely based on DFT calculations, could be falsified.

| S-EPMC10084129 | 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