Divergent Construction of Spirocyclopentene-3,2′-indolines with Vicinal Stereocenters via Palladium-Catalyzed Aza-Wacker Cyclization

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

Published: April 14, 2025

Herein, we report an aerobic palladium-catalyzed aza-Wacker cyclization to produce spirocyclopentene-3,2'-indolines with vicinal stereocenters. Using 1,2-bis(diphenylphosphino)benzene (dppbz) and pyridine as ligands, achieved a ligand-modulated diastereodivergent synthesis, producing cis- trans-spirocyclopentene-3,2'-indolines exceptional yields diastereoselectivities. Density functional theory (DFT) calculations revealed that selective proceeds through distinct trans- cis-aminopalladation mechanisms.

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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CuI-Catalyzed Dearomatization/Peroxidation/Cyclization Cascade of Pyrrole-Tethered Indoles

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 27, 2025

A mild CuI-catalyzed dearomatization/peroxidation/cyclization cascade of pyrrole-tethered indoles has been reached, providing peroxide-incorporated indolizino[8,7-b]indole derivatives in acceptable to good yields (46–76%). Dehydrogenated peroxide can be obtained by the use a FeCl3/TBHP (tBuOOH)/2,2,2-trifluoroethanol (TFE) system at 50 °C.

Language: Английский

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Divergent and Enantioselective Synthesis of Three Types of Chiral Polycyclic N-Heterocycles via Copper-Catalyzed Dearomative Cyclization

ACS Central Science, Journal Year: 2025, Volume and Issue: 11(5), P. 805 - 815

Published: May 2, 2025

Significant advancements have been made in the catalytic asymmetric dearomatization of indoles for constructing valuable chiral polycyclic N-heterocycles. However, dearomative cyclopropanation continues to pose a formidable challenge. Furthermore, diverse transformations indoline-fused cyclopropanes via strain release remain largely unexplored, potentially unveiling new chemistry. Here, we disclose Cu-catalyzed indole-diynes and subsequent [3 + 2] cycloaddition with oxygen, facilitating divergent atom-economical synthesis enantioenriched cyclopropane- 1,2-dioxolane-fused indolines moderate excellent yields generally outstanding diastereo- enantioselectivities broad substrate scope. Importantly, this protocol not only represents first utilizing alkynes as carbene precursors but also constitutes construction 1,2-dioxolanes high stereoselectivity. Interestingly, Brønsted acid-promoted ring-opening rearrangement cyclopropane-fused display distinctive chemoselectivity afford cyclohepta-[b]-indoles good efficiency enantiocontrol. In addition, both potential reaction pathways origins control within tandem sequence are robustly supported by experiments theoretical calculations.

Language: Английский

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Palladium-catalyzed intermolecular asymmetric dearomatizative arylation of indoles and benzofurans

Science Advances, Journal Year: 2025, Volume and Issue: 11(22)

Published: May 30, 2025

Indoles represent one of the most robust and synthetically versatile classes heteroaromatic compounds. However, stereoselective conversion planar indole rings into three-dimensional indoline skeletons bearing multiple stereogenic centers remains a persistent challenge in organic synthesis. Herein, we describe an intermolecular catalytic asymmetric dearomatization simple indoles via palladium-catalyzed three-component cross-coupling reaction. By using readily accessible diazonium salts aromatic boronic acids as arylative reagents under ligand-swap strategy, this method enables efficient construction 2,3-diarylated indolines. Mechanistic studies reveal that chiral BiOx ligand governs highly migratory insertion aryl-palladium intermediate indole’s C═C double bond with complete diastereo- regioselectivity, whereas achiral fumarate facilitates reductive elimination step, corroborated by density functional theory calculations. Furthermore, protocol is extended to dearomative diarylation benzofurans, affording 2,3-dihydrobenzofuran derivatives high stereocontrol.

Language: Английский

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Synthesis of indolizines via Pd-catalyzed selective ring recasting of oxazolidines with deesterification of methyl acrylates

Sustainable Chemistry and Pharmacy, Journal Year: 2025, Volume and Issue: 46, P. 102059 - 102059

Published: June 5, 2025

Language: Английский

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Catalytic Asymmetric Reactions of Ketimines and Alkenes via [2 + 2] Cycloaddition: Chemical Reactivity Controlled by Switching a Heteroatom

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(46), P. 32088 - 32097

Published: Nov. 8, 2024

Azetidine units are commonly found in natural products and biologically active drugs. The [2 + 2] cycloaddition of imines alkenes has been extensively used the synthesis such structures, while enantioselective approaches remain elusive. Herein, an efficient B(C

Language: Английский

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Mechanistic Investigation of the Pseudo-Halogen Effect in Enantioselective Aminocatalyzed [6 + 4] and [10 + 6] Cycloadditions: Enabling Unique Favorskii-Like Rearrangements

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 28, 2024

A mechanistic investigation into the novel combination of

Language: Английский

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