Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Chiral Phosphoric Acid Catalyzed Conversion of Epoxides into Thiiranes: Mechanism, Stereochemical Model, and New Catalyst Design.

ABSTRACT: Computations and experiments leading to new chiral phosphoric acids (CPAs) for epoxide thionations are reported. Density functional theory calculations reveal the mechanism and origin of the enantioselectivity of such CPA-catalyzed epoxide thionations. The calculated mechanistic information was used to design new efficient CPAs that were tested experimentally and found to be highly effective. Bulky ortho-substituents on the 3,3'-aryl groups of the CPA are important to restrict the position of the epoxide in the key transition states for the enantioselectivity-determining step. Larger para-substituents significantly improve the enantioselectivity of the reaction.

SUBMITTER: Duan M

PROVIDER: S-EPMC9305870 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Chiral Phosphoric Acid Catalyzed Conversion of Epoxides into Thiiranes: Mechanism, Stereochemical Model, and New Catalyst Design.

Duan Meng M Díaz-Oviedo Christian David CD Zhou Yang Y Chen Xiangyang X Yu Peiyuan P List Benjamin B Houk Kendall N KN Lan Yu Y

Angewandte Chemie (International ed. in English) 20220114 9

Computations and experiments leading to new chiral phosphoric acids (CPAs) for epoxide thionations are reported. Density functional theory calculations reveal the mechanism and origin of the enantioselectivity of such CPA-catalyzed epoxide thionations. The calculated mechanistic information was used to design new efficient CPAs that were tested experimentally and found to be highly effective. Bulky ortho-substituents on the 3,3'-aryl groups of the CPA are important to restrict the position of th ...[more]

PMID: 34889494

Similar Datasets

Chiral phosphoric acid catalyzed peroxidation of imines.

Project description: Not available

| S-EPMC2941208 | biostudies-literature

F<sub>10</sub>BINOL-derived chiral phosphoric acid-catalyzed enantioselective carbonyl-ene reaction: theoretical elucidation of stereochemical outcomes.

Project description:An F10BINOL-derived chiral phosphoric acid was shown to be an effective catalyst for an enantioselective carbonyl-ene reaction of 1,1-disubstituted olefins with ethyl glyoxylate as the common enophile. The perfluoro-binaphthyl skeleton is beneficial not only for adopting high catalytic activity but also for creating an effective chiral environment for enantioselective transformations. Indeed, the reaction afforded enantio-enriched homoallylic alcohols in high yields with high enantioselectivities. Theoretical studies identified that the multi-point C-H···O hydrogen bonds and the π interactions between the substrates and the 6-methoxy-2-naphthyl substituents at the 3,3'-positions of the F10BINOL skeleton play a crucial role in determining the stereochemical outcomes. The significance of the perfluoro-binaphthyl skeleton in achieving the high enantioselectivity was also evaluated through a structural analysis of the catalysts.

| S-EPMC6354837 | biostudies-literature

Phosphoric acid-catalyzed atroposelective construction of axially chiral arylpyrroles.

Project description:Axially chiral arylpyrroles are key components of pharmaceuticals and natural products as well as chiral catalysts and ligands for asymmetric transformations. However, the catalytic enantioselective construction of optically active arylpyrroles remains a formidable challenge. Here we disclose a highly efficient strategy to access enantioenriched axially chiral arylpyrroles by means of organocatalytic atroposelective desymmetrization and kinetic resolution. Depending on the remote control of chiral catalyst, the arylpyrroles were obtained in high yields and excellent enantioselectivities under mild reaction conditions. This strategy tolerates a wide range of functional groups, providing a facile avenue to approach axially chiral arylpyrroles from simple and readily available starting materials. Selected arylpyrrole products proved to be efficient chiral ligands in asymmetric catalysis and also important precursors for further synthetic transformations into highly functionalized pyrroles with potential bioactivity, especially the axially chiral fully substituted arylpyrroles.

| S-EPMC6361918 | biostudies-literature

Chiral phosphoric acid-catalyzed enantioselective construction of structurally diverse benzothiazolopyrimidines.

Project description:A highly efficient catalytic enantioselective [4+2] cycloaddition was developed between 2-benzothiazolimines and enecarbamates. A wide range of benzothiazolopyrimidines bearing three contiguous stereogenic centers was obtained in high to excellent yields and with excellent diastereo- and enantioselectivities (d.r. > 98 : 2 and up to >99% ee). Furthermore, this chiral phosphoric acid-catalyzed strategy was scalable and enabled access to a new class of optically pure Lewis base isothiourea derivatives.

| S-EPMC6461124 | biostudies-literature

Asymmetric Synthesis of Griffipavixanthone Employing a Chiral Phosphoric Acid-Catalyzed Cycloaddition.

Project description:Asymmetric synthesis of the biologically active xanthone dimer griffipavixanthone is reported along with its absolute stereochemistry determination. Synthesis of the natural product is accomplished via dimerization of a p-quinone methide using a chiral phosphoric acid catalyst to afford a protected precursor in excellent diastereo- and enantioselectivity. Mechanistic studies, including an unbiased computational investigation of chiral ion-pairs using parallel tempering, were performed in order to probe the mode of asymmetric induction.

| S-EPMC6475489 | biostudies-literature

Synthesis of Lactams via a Chiral Phosphoric Acid-Catalyzed Aniline Cyclization.

Project description:The enantioenriched lactams disclosed in this work are synthesized concisely in four steps. In the penultimate reaction, a benzylamine species complexes with a chiral phosphoric acid to produce benzo-fused δ-lactams equipped with an all-carbon quaternary stereocenter. Partial and full reductions were carried out on the ester and amide moieties, and a Suzuki-Miyaura cross-coupling expanded the molecule from the aromatic ring. Finally, our method was successful at a >1 g scale, indicating that the method has important practical use.

| S-EPMC11382273 | biostudies-literature

Chiral phosphoric acid-catalyzed desymmetrization of meso-aziridines with functionalized mercaptans.

Project description:Conditions for the phosphoric acid-catalyzed highly enantioselective ring-opening of meso-aziridines with a series of functionalized aromatic thiol nucleophiles are described. The procedure utilizes commercially available aromatic thiols, a series of meso-aziridines, and a catalytic amount of VAPOL phosphoric acid to explore the substrate scope of this highly enantioselective reaction.

| S-EPMC2780433 | biostudies-literature

Chiral phosphoric acid-catalyzed enantioselective phosphinylation of 3,4-dihydroisoquinolines with diarylphosphine oxides.

Project description:Chiral phosphorous-containing compounds are playing a more and more significant role in several different research fields. Here, we show a chiral phosphoric acid-catalyzed enantioselective phosphinylation of 3,4-dihydroisoquinolines with diarylphosphine oxides for the efficient and practical construction of a family of chiral α-amino diarylphosphine oxides with a diverse range of functional groups. The phosphine products are suitable for transforming to several kinds of chiral (thio)ureas, which might be employed as chiral ligands or catalysts with potential applications in asymmetric catalysis. Control and NMR tracking experiments show that the reaction proceeds via the tert-butyl 1-(tert-butoxy)-3,4-dihydroiso-quinoline-2(1H)-carboxylate intermediate, followed by C-P bond formation. Furthermore, computational studies elucidated that the hydrogen bonding strength between the phosphonate and isoquinolinium determines the stereoselectivity of the phosphinylation reaction.

| S-EPMC9911717 | biostudies-literature

Chiral phosphoric acid catalyzed aminative dearomatization of α-naphthols/Michael addition sequence.

Project description:Asymmetric dearomatization reactions have recently emerged as a powerful tool for the rapid build-up of the molecular complexity. Chiral three-dimensional polycyclic molecules bearing contiguous stereogenic centers can be synthesized from readily available planar aromatic feedstocks. Here we report that an intermolecular asymmetric dearomatization reaction of α-naphthols bearing a tethered nucleophile at the C4 position of the naphthol ring is achieved by a chiral phosphoric acid. The reaction proceeds via a highly chemo- and regioselective aminative dearomatization/Michael addition sequence, affording a wide array of functionalized cyclic ketones in good yields (up to 93%) with excellent enantioselectivity (up to >99% ee). The catalyst loading can be reduced to 0.1 mol%. Preliminary mechanistic investigations identify that the enantioselectivity is established in the dearomatization step, while the Michael addition is the rate-limiting step. A working model accounting for the origin of the stereochemistry is proposed based on DFT calculations.

| S-EPMC6637135 | biostudies-literature

Chiral spirocyclic phosphoric acid-catalyzed enantioselective synthesis of heterotriarylmethanes bearing an amino acid moiety.

Project description:We present herein an enantioselective protocol for the chiral phosphoric acid-catalyzed addition of 3-arylisoxazol-5-amines to highly reactive 3-methide-3H-pyrroles to provide a diverse range of heterotriarylmethanes bearing an amino acid moiety in good yields (up to 97%) and high enantioselectivities (up to 93% ee) under mild conditions. The chiral spirocyclic phosphoric acid is crucial in converting the initial 1H-pyrrol-3-yl carbinols into reactive 3-methide-3H-pyrroles and obtaining the good enantiocontrol, thereby facilitating the desired enantioselective transformation.

| S-EPMC10285616 | 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