Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Chirality Transfer and Asymmetric Catalysis: Two Strategies toward the Enantioselective Formal Total Synthesis of (+)-Gelsenicine.

ABSTRACT: Two strategies are described en route to an enantioselective total synthesis of gelsenicine. One approach centers on a chirality transfer cycloisomerization that ultimately fell short. Separately, an asymmetric catalysis route utilizing bisphosphine-gold-catalyzed cycloisomerization was pursued. A catalytic system was identified that provided a synthetic intermediate in our Gelsemium alkaloid syntheses in high enantiopurity and with absolute configuration determined by electronic circular dichroism, thus representing an enantioselective formal total synthesis of (+)-gelsenicine.

SUBMITTER: Knutson PC

PROVIDER: S-EPMC9297687 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Chirality Transfer and Asymmetric Catalysis: Two Strategies toward the Enantioselective Formal Total Synthesis of (+)-Gelsenicine.

Knutson Phil C PC Ji Haofan H Harrington Christopher M CM Ke Yan-Ting YT Ferreira Eric M EM

Organic letters 20220707 27

Two strategies are described en route to an enantioselective total synthesis of gelsenicine. One approach centers on a chirality transfer cycloisomerization that ultimately fell short. Separately, an asymmetric catalysis route utilizing bisphosphine-gold-catalyzed cycloisomerization was pursued. A catalytic system was identified that provided a synthetic intermediate in our <i>Gelsemium</i> alkaloid syntheses in high enantiopurity and with absolute configuration determined by electronic circular ...[more]

PMID: 35796493

Similar Datasets

The Analysis of Two Distinct Strategies toward the Enantioselective Formal Total Synthesis of (+)-Gelsenicine.

Project description:A full account of a formal enantioselective total synthesis of (+)-gelsenicine is described. Separate strategies based on catalytic cycloisomerization as the central step are considered. One plan involves chirality transfer from enantioenriched substrates, while the other employs asymmetric catalysis. The chirality transfer strategy is less effective, while in the latter, phosphoramidite- and bisphosphine-gold complexes are tested and ultimately provide a key intermediate in high enantiopurity in our Gelsemium alkaloid syntheses.

| S-EPMC10077972 | biostudies-literature

Enantioselective Total Synthesis of (-)-Finerenone Using Asymmetric Transfer Hydrogenation.

Project description:(-)-Finerenone is a nonsteroidal mineralocorticoid receptor antagonist currently in phase III clinical trials for the treatment of chronic kidney disease in type 2 diabetes. It contains an unusual dihydronaphthyridine core. We report a 6-step synthesis of (-)-finerenone, which features an enantioselective partial transfer hydrogenation of a naphthyridine using a chiral phosphoric acid catalyst with a Hantzsch ester. The process is complicated by the fact that the naphthyridine exists as a mixture of two atropisomers that react at different rates and with different selectivities. The intrinsic kinetic resolution was converted into a kinetic dynamic resolution at elevated temperature, which enabled us to obtain (-)-finerenone in both high yield and high enantioselectivity. DFT calculations have revealed the origin of selectivity.

| S-EPMC7839499 | biostudies-literature

Enantioselective formal (3 + 3) cycloaddition of bicyclobutanes with nitrones enabled by asymmetric Lewis acid catalysis.

Project description:The absence of catalytic asymmetric methods for synthesizing chiral (hetero)bicyclo[n.1.1]alkanes has hindered their application in new drug discovery. Here we demonstrate the achievability of an asymmetric polar cycloaddition of bicyclo[1.1.0]butane using a chiral Lewis acid catalyst and a bidentate chelating bicyclo[1.1.0]butane substrate, as exemplified by the current enantioselective formal (3 + 3) cycloaddition of bicyclo[1.1.0]butanes with nitrones. In addition to the diverse bicyclo[1.1.0]butanes incorporating an acyl imidazole group or an acyl pyrazole moiety, a wide array of nitrones are compatible with this Lewis acid catalysis, successfully assembling two congested quaternary carbon centers and a chiral aza-trisubstituted carbon center in the pharmaceutically important hetero-bicyclo[3.1.1]heptane product with up to 99% yield and >99% ee.

| S-EPMC11393060 | biostudies-literature

Formal nucleophilic pyrrolylmethylation <i>via</i> palladium-based auto-tandem catalysis: switchable regiodivergent synthesis and remote chirality transfer.

Project description:Although nucleophilic benzylation-type reaction to introduce various aromatic systems into molecules has been widely explored, the related pyrrolylmethylation version remains to be disclosed. Reported herein is a palladium-catalysed multiple auto-tandem reaction between N-Ts propargylamines, allyl carbonates and aldimines in the presence of an acid, proceeding through sequential allylic amination, cycloisomerisation, vinylogous addition and aromatisation steps. A diversity of formal pyrrolylmethylated amine products were finally furnished efficiently. In addition, switchable regiodivergent 3-pyrrolylmethylation and 4-pyrrolylmethylation were realised by tuning catalytic conditions. Moreover, remote chirality transfer with readily available enantioenriched starting materials was well achieved with an achiral ligand, relying on diastereoselective generation of η2-Pd(0) complexes between Pd(0) and chiral 1,3-diene intermediates in the key vinylogous addition step. A few control experiments were conducted to elucidate the palladium-involved tandem reaction and regiodivergent synthesis.

| S-EPMC9628985 | biostudies-literature

Enantioselective formal total synthesis of (+)-aspergillide C.

Project description:An enantioselective formal total synthesis of the cytotoxic macrolide (+)-aspergillide C has been accomplished from (S)-(-)-glyceraldehyde acetonide and the Danishefsky-Kitahara diene. Strategic transformations include a hetero Diels-Alder reaction, Ferrier-type addition, and palladium-catalyzed oxidative lactonization to set key stereocenters within the dihydropyran core, followed by fragment coupling via (E)-selective Julia-Kocienski olefination.

| S-EPMC2783990 | biostudies-literature

Asymmetric Catalysis in Chiral Solvents: Chirality Transfer with Amplification of Homochirality through a Helical Macromolecular Scaffold.

Project description:Use of chiral solvents in asymmetric synthesis as a sole source of enantioselection remains largely unexplored in organic synthesis. We found that the use of a helical macromolecular catalyst of which helical chirality is dynamically formed in chiral solvents allowed several mechanistically different reactions to proceed with high enantioselectivity. In this system, the chirality of the solvent, such as limonene, induces a configurational imbalance to the helical macromolecular scaffold of the catalyst, and in turn to the reaction products through palladium-catalyzed asymmetric reactions including Suzuki-Miyaura cross-coupling (up to 98% ee), styrene hydrosilylation (up to 95% ee), and silaboration (up to 89% ee). Not only enantiomerically pure limonene but also limonene with low enantiomeric excesses induce single-handed helical structures with majority-rule-based amplification of homochirality. The helical conformation of the macromolecular catalyst was retained even in the absence of limonene in the solid state, enabling asymmetric cross-coupling in achiral solvent with high enantioselectivity.

| S-EPMC6661863 | biostudies-literature

Coordinative Alignment of Chiral Molecules to Control over the Chirality Transfer in Spontaneous Resolution and Asymmetric Catalysis.

Project description:The production and availability of enantiomerically pure compounds that spurred the development of chiral technologies and materials are very important to the fine chemicals and pharmaceutical industries. By coordinative alignment of enantiopure guests in the metal‒organic frameworks, we reported an approach to control over the chirality of homochiral crystallization and asymmetric transformation. Synthesized by achiral triphenylamine derivatives, the chirality of silver frameworks was determined by the encapsulated enantiopure azomethine ylides, from which clear interaction patterns were observed to explore the chiral induction principles. With the changing of addition sequence of substrates, the enantioselectivity of asymmetric cycloaddition was controlled to verify the determinant on the chirality of the bulky MOF materials. The economical chirality amplification that merges a series of complicated self-inductions, bulk homochiral crystallization and enantioselective catalysis opens new avenues for enantiopure chemical synthesis and provides a promising path for the directional design and development of homochiral materials.

| S-EPMC5684417 | biostudies-literature

Dynamic control of chirality in phosphine ligands for enantioselective catalysis.

Project description:Chirality plays a fundamental role in biology and chemistry and the precise control of chirality in a catalytic conversion is a key to modern synthesis most prominently seen in the production of pharmaceuticals. In enantioselective metal-based catalysis, access to each product enantiomer is commonly achieved through ligand design with chiral bisphosphines being widely applied as privileged ligands. Switchable phosphine ligands, in which chirality is modulated through an external trigger signal, might offer attractive possibilities to change enantioselectivity in a catalytic process in a non-invasive manner avoiding renewed ligand synthesis. Here we demonstrate that a photoswitchable chiral bisphosphine based on a unidirectional light-driven molecular motor, can be used to invert the stereoselectivity of a palladium-catalysed asymmetric transformation. It is shown that light-induced changes in geometry and helicity of the switchable ligand enable excellent selectivity towards the racemic or individual enantiomers of the product in a Pd-catalysed desymmetrization reaction.

| S-EPMC4389239 | biostudies-literature

Chirality-assisted lateral momentum transfer for bidirectional enantioselective separation.

Project description:Lateral optical forces induced by linearly polarized laser beams have been predicted to deflect dipolar particles with opposite chiralities toward opposite transversal directions. These "chirality-dependent" forces can offer new possibilities for passive all-optical enantioselective sorting of chiral particles, which is essential to the nanoscience and drug industries. However, previous chiral sorting experiments focused on large particles with diameters in the geometrical-optics regime. Here, we demonstrate, for the first time, the robust sorting of Mie (size ~ wavelength) chiral particles with different handedness at an air-water interface using optical lateral forces induced by a single linearly polarized laser beam. The nontrivial physical interactions underlying these chirality-dependent forces distinctly differ from those predicted for dipolar or geometrical-optics particles. The lateral forces emerge from a complex interplay between the light polarization, lateral momentum enhancement, and out-of-plane light refraction at the particle-water interface. The sign of the lateral force could be reversed by changing the particle size, incident angle, and polarization of the obliquely incident light.

| S-EPMC7160209 | biostudies-literature

Catalytic Asymmetric Formal Total Synthesis of (-)-Triptophenolide and (+)-Triptolide.

Project description:Catalytic asymmetric formal synthesis of (-)-Triptophenolide and (+)-Triptolide have been achieved. Key reaction involves Palladium catalyzed asymmetric conjugate addition of aryl boronic acid to 3-methyl cyclohexe-1-none to form quaternary carbon. Claisen rearrangement and subsequent aldol reaction furnished trans-decaline key intermediate, which assured a formal total synthesis of (-)-Triptophenolide and (+)-Triptolide.

| S-EPMC5385656 | 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