Recent advances in the catalytic asymmetric construction of axially chiral azole-based frameworks DOI
Weiwei Luo, Yu Zhang,

Meijun Ming

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(23), P. 6819 - 6849

Published: Jan. 1, 2024

This review highlights recent advances in the atroposelective preparation of axially chiral azole derivatives, emphasizing mechanistic insights and synthetic applications development this class five-membered heterocyclic frameworks.

Language: Английский

Topology-Directed Synthesis of Helical Phosphoniums with High Diradical Character and Polar-Dependent Electron Transfer DOI Creative Commons
Bo Yang,

Suqiong Yan,

Shirong Ban

et al.

Published: June 7, 2024

Molecular topology synthesis of polycyclic aromatic heterocycles (PAHs) with diradical character takes root in the intramolecular coupling breakthrough. Herein, we report selectively Mn(III)/Cu(II)-mediated C−P and C−H bond cleavage to obtain robust donorfused phosphoniums helical or planar geometries distinct cationic charges. The former structures incorporate a common phospha[5]helication acceptor different arylamines donors, latter one contains phospha[6]dication same donors. These unprecedented donor-acceptor (D−A) pairs show unique topology-dependent optoelectronic properties. folded radical centers possess an extreme electron-deficient state throughspace isolation high (y0 = 0.989). Moreover, ingenious charge transfer (CT) locally excited (LE) transition components facilitate diverse hybridized local (HLCT) solvents, endowing highest emission bandgap variation 0.78 eV (~217 nm). could also be adjusted from blue near-infrared regions via tailoring polardependent HLCT, which output additional circularly polarized luminescence compatible chiral menthol matrix elevated quantum efficiency retained deep-red glow. It is worth mentioning that atomically precise Mn(III) halide has been unprecedentedly captured determined for activation

Language: Английский

Citations

2
Catalytic Atroposelective Synthesis of C−N Axially Chiral Aminophosphines via Dynamic Kinetic Resolution DOI
Carlos Rodríguez-Franco, Esther Roldán‐Molina, Alberto Aguirre‐Medina

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(37)

Published: June 25, 2024

A ruthenium-catalyzed reductive amination via asymmetric transfer hydrogenation (ATH) has been used to perform an efficient dynamic kinetic resolution (DKR) of N-aryl 2-formyl pyrroles decorated with a phosphine moiety positioned at the ortho' position. The strategy relies on labilization stereogenic axis in substrate facilitated by transient Lewis acid-base interaction (LABI) between carbonyl carbon and phosphorus center. reaction features broad scope aliphatic amines pyrrole scaffolds, proceeds under very mild conditions afford P,N atropisomers good high yields excellent enantioselectivities (up 99 % ee) for both diphenyl dicyclohexylphosphino derivatives.

Language: Английский

Citations

2
Symmetric Anion Mediated Dynamic Kinetic Asymmetric Knoevenagel Reaction for N−C and N−N Atropisomers Synthesis DOI

Hongyu Qu,

Chenyang Huo,

Jimeng Ge

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 21, 2024

A symmetric anion mediated dynamic kinetic asymmetric Knoevenagel reaction was established as a general and efficient method for accessing both N-C N-N atropisomers. The resulting highly enantio-pure pyridine-2,6(1H,3H)-diones exhibit diverse structures functional groups. key to excellent regio- remote enantiocontrol could be owed the hydrogen bond between enolate triflamide block of organocatalyst. This connected iminium cation by chiral backbone. mechanism investigation via control experiments, correlation analysis, density theory calculations further revealed how stereochemical information transferred from catalyst into axially pyridine-2,6(1H,3H)-diones. synthetic applications also demonstrated reaction's potential.

Language: Английский

Citations

2
Catalytic Atroposelective Construction of Furan‐Based Axially Chiral Scaffolds DOI

Wei Tan,

Xinyue Wu, Feng Shi

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(21)

Published: July 19, 2024

Abstract Axially chiral furan‐based scaffolds have been recognized as a class of important five‐membered heteroaryl atropisomers, and developing catalytic atroposelective reactions for constructing this is highly desirable. However, the construction such rather underdeveloped due to existence great challenges remote ortho ‐substituents weak configurational stability. To overcome these challenges, synthetic chemists recently paid attention research field, number axially constructed via using different strategies. This concept summarized advances in field pointed out remaining which will promote further development emerging field.

Language: Английский

Citations

2
Recent advances in the catalytic asymmetric construction of axially chiral azole-based frameworks DOI
Weiwei Luo, Yu Zhang,

Meijun Ming

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(23), P. 6819 - 6849

Published: Jan. 1, 2024

This review highlights recent advances in the atroposelective preparation of axially chiral azole derivatives, emphasizing mechanistic insights and synthetic applications development this class five-membered heterocyclic frameworks.

Language: Английский

Citations

2