Enantioselective Rhodium‐Catalyzed C−H Arylation Enables Direct Synthesis of Atropisomeric Phosphines DOI
Zexian Li,

Weipeng Xu,

Shuaishuai Song

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(8)

Published: Jan. 6, 2024

Abstract Atropisomeric phosphines hold considerable significance in asymmetric catalysis, yet their synthesis presents a formidable challenge owing to intricate multistep procedures. In this context, groundbreaking methodology has been presented for preparation. This innovative approach entails an atroposelective rhodium‐catalyzed C−H activation employing aryl and heteroaryl halides, chelated by P(III) center. The essence of strategy lies its ability directly construct chiral phosphine ligands single step, thereby exhibiting exceptional efficiency terms atom redox economy. Illustrative examples serve demonstrate the immense potential situ‐formed catalysis. Mechanistic experiments have further provided invaluable insights into transformation.

Language: Английский

Enantioselective Access to Triaryl-2-pyrones with Monoaxial or Contiguous C–C Diaxes via Oxidative NHC Catalysis DOI

Si-Chen Zhang,

Shengping Liu, Xia Wang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(4), P. 2565 - 2575

Published: Feb. 6, 2023

We present herein an unprecedented stereoselective synthesis of triaryl-2-pyrones with monoaxial or contiguous diaxes from readily available starting materials. This N-heterocyclic carbene catalysis method adopts atroposelective annulation 2-aryketones ynals under oxidative conditions. The includes the construction one two axes in a single operation, achieves step economy, and affords axially chiral moderate to good yields, high excellent enantioselectivities. DFT calculations relative energies stereoisomers rotational barriers were performed.

Language: Английский

Citations

43
Diastereo- and atroposelective synthesis of N-arylpyrroles enabled by light-induced phosphoric acid catalysis DOI Creative Commons
Lei Dai, Xueting Zhou, Jiami Guo

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Aug. 9, 2023

The C-N axially chiral N-arylpyrrole motifs are privileged scaffolds in numerous biologically active molecules and natural products, as well ligands/catalysts. Asymmetric synthesis of N-arylpyrroles, however, is still challenging, the simultaneous creation contiguous axial central chirality remains unknown. Herein, a diastereo- atroposelective N-arylpyrroles enabled by light-induced phosphoric acid catalysis has been developed. key transformation one-pot, three-component oxo-diarylation reaction, which simultaneously creates quaternary stereogenic center. A broad range unactivated alkynes were readily employed reaction partner this transformation, products obtained good yields, with excellent enantioselectivities very diastereoselectivities. Notably, skeletons represent interesting structural that could be used ligands catalysts asymmetric catalysis.

Language: Английский

Citations

29
Developing Biarylhemiboronic Esters for Biaryl Atropisomer Synthesis via Dynamic Kinetic Atroposelective Suzuki–Miyaura Cross-Coupling DOI

Yiming Yang,

Changhui Wu,

Junhao Xing

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(9), P. 6283 - 6293

Published: Feb. 21, 2024

We herein introduce biarylhemiboronic esters as a new type of bridged biaryl reagent for asymmetric synthesis axially chiral structures, and the palladium-catalyzed Suzuki-Miyaura cross-coupling is developed. This dynamic kinetic atroposelective coupling reaction exhibits high enantioselectivity, good functional group tolerance, broad substrate scope. The synthetic application current method was demonstrated by transformations product programmed polyarene. Preliminary mechanistic studies suggested that proceeded via an enantio-determining transmetalation step.

Language: Английский

Citations

16
Mechanism and Origin of Stereoselectivity for the NHC-Catalyzed Desymmetrization Reaction for the Synthesis of Axially Chiral Biaryl Aldehydes DOI
Xiaoxiao Hou, Donghui Wei

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(5), P. 3133 - 3142

Published: Feb. 15, 2024

Organocatalytic desymmetrization reaction is a powerful tool for constructing axial chirality, but the theoretical study on origin of stereoselectivity still lags behind even now. In this work, N-heterocyclic carbene (NHC)-catalyzed biaryl frameworks synthesis axially chiral aldehydes has been selected and theoretically investigated by using density functional theory (DFT). The fundamental pathway involves several steps, i.e., desymmetrization, formation Breslow oxidation, esterification, NHC regeneration. processes have identified as stereoselectivity-determining rate-determining steps. Further weak interaction analyses proved that C–H···O hydrogen bond C–H···π interactions are responsible stability key stereoselective transition states. This research contributes to understanding nature NHC-catalyzed reactions compounds.

Language: Английский

Citations

14
Enantioselective Rhodium‐Catalyzed C−H Arylation Enables Direct Synthesis of Atropisomeric Phosphines DOI
Zexian Li,

Weipeng Xu,

Shuaishuai Song

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(8)

Published: Jan. 6, 2024

Atropisomeric phosphines hold considerable significance in asymmetric catalysis, yet their synthesis presents a formidable challenge owing to intricate multistep procedures. In this context, groundbreaking methodology has been presented for preparation. This innovative approach entails an atroposelective rhodium-catalyzed C-H activation employing aryl and heteroaryl halides, chelated by P(III) center. The essence of strategy lies its ability directly construct chiral phosphine ligands single step, thereby exhibiting exceptional efficiency terms atom redox economy. Illustrative examples serve demonstrate the immense potential situ-formed catalysis. Mechanistic experiments have further provided invaluable insights into transformation.

Language: Английский

Citations

10
Asymmetric synthesis of stereogenic-at-iridium(III) complexes through Pd-catalyzed kinetic resolution DOI Creative Commons
Yunpeng Chu,

Xue‐Lin Yue,

De‐Hai Liu

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 30, 2025

Metal-centered chirality has been recognized for over one century, and stereogenic-at-metal complexes where is exclusively attributed to the metal center due specific coordination pattern of achiral ligands around ion, broadly utilized in diverse areas natural science. However, synthesis these molecules remains constrained. Notably, while asymmetric catalysis played a crucial role production optically active organic molecules, its application less straightforward. In this study, we introduce kinetic resolution strategy employing Pd-catalyzed Suzuki-Miyaura cross-coupling reaction that efficiently produces stereogenic-at-iridium from racemic mixtures with high selectivity (achieving an s-factor up 133). This method enables further relevant chiral metallodrugs photosensitizers, underscoring practical utility our approach. Mechanistic studies suggest reductive elimination likely turnover-limiting step cross-coupling.

Language: Английский

Citations

1
Dual Catalytic C(sp2)–H Activation of Azaheterocycles toward C–N Atropisomers DOI
Juntao Sun, Yiyao Hu, Wen‐Ji He

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3700 - 3710

Published: Feb. 14, 2025

Language: Английский

Citations

1
Enantioselective construction of inherently chiral pillar[5]arenes via palladium-catalysed Suzuki–Miyaura cross-coupling DOI Creative Commons

T. Luan,

Che Sun,

Yongle Tian

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 10, 2025

Pillar[n]arenes have broad applications in biological medicine, materials science, and supramolecular gels. Notably, enantiopure pillar[5]arenes are valued for their roles enantioselective host–guest recognition, chiral sensing, asymmetric catalysis, related fields. Current methods obtaining pillar[n]arenes rely heavily on resolution agents or HPLC resolution. However, the synthesis of these compounds via catalysis remains challenging. In this study, we develop an extended side-arm Suzuki–Miyaura cross-coupling strategy to construct inherently with excellent yields high enantioselectivities using a palladium catalyst Sadphos ligand. The reaction scope extends beyond arylboronic acids encompass 2-arylvinylboronic other multi-OTf-substituted substrates, all efficiently producing desired products. Further exploration synthetic applications, along photophysical chiroptical analyses, confirm potential diverse across multiple disciplines. Enantiopure recognition but current Here, authors pillar[5]arenes.

Language: Английский

Citations

1
Synthesis of Axially Chiral Biaryls via Enantioselective Ullmann Coupling ofortho‐Chlorinated Aryl Aldehydes Enabled by a Chiral 2,2′‐Bipyridine Ligand DOI
Saima Perveen, Shuai Zhang, Linghua Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(47)

Published: Oct. 5, 2022

The first nickel-catalyzed highly enantioselective reductive Ullmann coupling of ortho-chlorinated aryl aldehyde was achieved under mild reaction conditions with a chiral 2,2'-bipyridine ligand (+)-DTB-SBpy, thus providing axially biphenyl or binaphthyl dials up to 99 % yield and 99.5:0.5 er. versatility the products as common synthetic intermediates for diverse ligands, catalysts, functional molecules demonstrated by short-step transformations. This protocol also allowed concise formal total synthesis biologically active natural (+)-kotanin, (-)-isoschizandrin (+)-gossypol.

Language: Английский

Citations

32
Organocatalytic Si–CAryl Bond Functionalization-Enabled Atroposelective Synthesis of Axially Chiral Biaryl Siloxanes DOI

Ming Jhang Wu,

Yi‐Wei Chen, Qian Lu

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(37), P. 20646 - 20654

Published: Sept. 11, 2023

Chiral organosilanes are valuable chemical entities in the development of functional organic materials, asymmetric catalysis, and medicinal chemistry. As an important strategy for constructing chiral organosilanes, functionalization Si-CAryl bond typically relies on transition-metal catalysis. Herein, we present efficient method atroposelective synthesis biaryl siloxane atropisomers via organocatalytic Si-C dinaphthosiloles with silanol nucleophiles. The reaction proceeds through protonation simultaneous cleavage/silanolysis sequence presence a newly developed Brønsted acid catalyst. versatile nature streamlines derivatization axially products into other atropisomers, thereby expanding applicability this method.

Language: Английский

Citations

21