Rhodium-catalyzed annulative approach to N–N axially chiral biarylsviaC–H activation and dynamic kinetic transformation

Chemical Science, Journal Year: 2023, Volume and Issue: 14(32), P. 8564 - 8569

Published: Jan. 1, 2023

N-N axially chiral biaryls represent a rarely explored class of atropisomeric compounds. We hereby report rhodium-catalyzed enantioselective [4 + 2] oxidative annulation internal alkynes with benzamides bearing two classes directing groups. The coupling occurs under mild conditions

Language: Английский

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Catalytic Asymmetric Synthesis of N−N Biaryl Atropisomers

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(2)

Published: Oct. 18, 2023

Atropisomers have emerged as important structural scaffolds in natural products, drug design, and asymmetric synthesis. Recently, N-N biaryl atropisomers drawn increasing interest due to their unique structure relatively stable axes. However, its synthesis remains scarce compared well-developed C-C analogs. In this concept, we summarize the of including pyrrole-pyrrole, pyrrole-indole, indole-indole, indole-carbazole, during which a series synthetic strategies are highlighted. Also, evolution is briefly reviewed an outlook offered.

Language: Английский

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Atroposelective Synthesis of Planar‐Chiral Indoles via Carbene Catalyzed Macrocyclization

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(3)

Published: Nov. 28, 2023

Abstract Indole‐based planar‐chiral macrocycles are widely found in natural products and bioactive molecules. However, sharp contrast to the preparation of indole‐based axially chiral structures, enantioselective catalysis is still a formidable task so far. Here we report an N ‐heterocyclic carbene (NHC)‐catalyzed intramolecular atroposelective macrocyclization 3‐carboxaldehyde indole/pyrroles, featuring with broad substrate scope good functional group tolerance, allowing for rapid access diverse indole/pyrrole‐based various tether‐lengths (10–16 members) yields excellent enantioselectivities. Importantly, macrocyclic structures both planar axial chirality were directly efficiently obtained through this protocol enantioselectivities diastereoselectivities. In addition, these synthesized offer many possibilities chemists develop new catalysts or ligands, as well reactions.

Language: Английский

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Ligand-Exchange-Enabled Axially Chiral Recognition in Asymmetric Aminopalladation/Olefination of 2-Alkynylanilides

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 4053 - 4065

Published: March 1, 2024

Chiral recognition for the synthesis of axially chiral biaryl units is a fundamental and challenging topic in organic synthesis. Herein, we documented that an efficient O-ligand exchange between catalyst substrate enabled axial asymmetric aminopalladation/olefination 2-alkynylanilides vinyl trifluoromethanesulfonates, providing 3-alkenylindoles with up to 97% ee 98% yield. This protocol features mild conditions, broad functional group tolerance, scalability, late-stage modification bioactive molecules. Experimental computational studies hinted (R)-BIDIME/Pd complex alkoxy was crucial success stereoselectivity control.

Language: Английский

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Enantioselective synthesis of tryptanthrin derivatives enabled by an asymmetric aza-Friedel–Crafts reaction

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(21), P. 5421 - 5427

Published: Jan. 1, 2023

A class of ketimines was first prepared and used in an asymmetric aza-Friedel–Crafts reaction for the highly enantioselective synthesis tryptanthrin derivatives.

Language: Английский

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Atroposelective Synthesis of C−N Vinylindole Atropisomers by Palladium‐Catalyzed Asymmetric Hydroarylation of 1‐Alkynylindoles

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)

Published: Sept. 25, 2023

Transition-metal-catalyzed hydroarylation of unsymmetrical internal alkynes remains challenging because the difficulty in controlling regioselectivity and stereoselectivity. Moreover, enantioselective using organoboron reagents has not been reported. Herein, we report for first time that palladium compounds can catalyze 1-alkynylindoles with organoborons synthesis chiral C-N atropisomers. A series rarely reported vinylindole atropisomers was synthesized excellent regio-, stereo- (Z-selectivity), enantioselectivity under mild reaction conditions. The ready availability simplicity, high stereoselectivity, good functional group tolerance this catalytic system make it highly attractive.

Language: Английский

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Multi-hydroxyl POSS supported iridium complexes as a recyclable catalyst for selective synthesis of N-/C-substituted indoles and the total synthesis of HIV-1 fusion inhibitor

Journal of Catalysis, Journal Year: 2023, Volume and Issue: 429, P. 115205 - 115205

Published: Nov. 24, 2023

Language: Английский

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Organocatalytic Enantioselective Friedel–Crafts Reaction of Phenanthrenequinones and Indoles

Molecules, Journal Year: 2025, Volume and Issue: 30(1), P. 172 - 172

Published: Jan. 4, 2025

An efficient stereoselective synthesis of 10-hydroxy-10-(1H-indol-3-yl)-9-(10H)-phenanthrene derivatives was realized through an organocatalyzed Friedel–Crafts reaction phenanthrenequinones and indoles using a (S,S)-dimethylaminocyclohexyl-squaramide as the catalyst. Under optimized conditions, desired chiral products were obtained in good yields (73–90%) with moderate to high ee values (up 97% ee). Two pairs synthesized enantiomers subjected evaluation their antiproliferative activities on four types human cancer cell lines one umbilical vein endothelial line CCK-8 assay. The results indicated that stereoselectivity had obvious impacts biological activity. (S)-4g found have optimal cytotoxicity against A549 safety profile for normal cells, which better than inhibitory activity positive control drug (doxorubicin).

Language: Английский

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Electrocatalytic Enantioselective Tandem C–H Indolization toward Biindolyl Atropisomers: Reaction Development and Mechanistic Insight

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1422 - 1430

Published: Jan. 9, 2025

The electrochemical methods for asymmetric indolization are still elusive and pose a significant challenge. Taking advantage of 2-alkynylanilines as electrochemically compatible indolyl equivalents, we herein represent mild highly enantioselective electrocatalytic process tandem C–H to form 2,3′-biindolyl atropisomers along with hydrogen evolution reaction. Integrated experimental computational mechanistic studies revealed that sequential metalation/nucleophilic cyclization/reductive elimination/anodic oxidation sequence involving RhIII–RhI–RhIII catalytic cycle accounts the established transformation.

Language: Английский

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Stereoselective Intramolecular Oxypalladation of Cyclic 1,3-Dione-Tethered Alkynes

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 13, 2025

An unconventional, highly stereoselective, and regioselective intramolecular oxypalladation/acyloxylation cascade of alkyne-tethered cyclic 1,3-diones has been developed. This atom-economic Pd(II)-catalyzed annulation reaction is initiated by the oxypalladation alkyne with an internal carbonyl group via 5-exo-dig cyclization instead conventional acetoxypalladation pathway. In this process, carboxylic acid plays a pivotal role in generation active cationic Pd-complex subsequent acyloxylation proto-demetalation steps. Additionally, method enables asymmetric using chiral bidentate BOX ligand, achieving enantiomeric ratios ≤93:7.

Language: Английский

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