Palladium/Norbornene Cooperative Catalysis 2-Fold C–H/C–X Coupling: Construction of Polycyclic Aromatic Hydrocarbons from Brominated Benzimidazoles

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

Published: March 10, 2025

A palladium/norbornene (NBE)-catalyzed 2-fold C-H/C-X coupling reaction of aryl iodides is reported. Bromine-substituted benzimidazoles were chosen as electrophilic and termination reagents, the versatile polycyclic aromatic hydrocarbon products successfully obtained. The strategy overcomes challenge catalyst poisoning by heterocyclic substrates. In addition, imidazole moiety in product endowed with a localization role, thus enabling compounds to be applied wider synthetic scenario, fluorescence persisted. Furthermore, bioactivity evaluation has identified three promising leading 3b, 4e, 4i.

Language: Английский

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A switch strategy for the synthesis of C4-ethylamine indole and C7-aminoindoline via controllable carbon elimination

Chemical Science, Journal Year: 2024, Volume and Issue: 15(39), P. 16169 - 16175

Published: Jan. 1, 2024

Controllable β-carbon elimination to extrude norbornene remains a long-standing challenge in palladium and chemistry. Herein, this manuscript describes switchable synthesis of biologically active C4-ethylaminoindole C7-aminoindoline scaffolds by controlling elimination, utilizing aziridine as C-H ethylamination reagent through C-N bond cleavage reaction. Furthermore, the protecting groups product can be easily removed, offering an unusual method for dopamine receptor agonists.

Language: Английский

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Rhodium-catalyzed atropodivergent hydroamination of alkynes by leveraging two potential enantiodetermining steps

Science Advances, Journal Year: 2024, Volume and Issue: 10(48)

Published: Nov. 27, 2024

A pair of enantiomers is known to have different biological activities. Two catalysts with opposite chirality are nearly always required deliver both enantiomeric products. In this work, chiral rhodium(III) cyclopentadienyl complexes repurposed as efficient for enantiodivergent and atroposelective hydroamination sterically hindered alkynes. Products been obtained using the same or closely analogous catalyst in good efficiency excellent enantioselectivity, enantiodivergence was mainly enabled by an achiral carboxylic acid its silver salt. Mechanistic studies revealed origin ascribable switch enantiodetermining step (alkyne insertion versus protonolysis) under control, which constitutes a previously unidentified working mode leveraging two elementary steps.

Language: Английский

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Palladium-Catalyzed Enantioselective Synthesis of P(V)-Stereogenic Compounds via Desymmetric Annulation of Prochiral Phosphinamides and Aryl Iodides

Organic Letters, Journal Year: 2024, Volume and Issue: 27(1), P. 121 - 128

Published: Dec. 30, 2024

The enantioselective synthesis of P(V)-stereogenic compounds has emerged as an interesting research topic primarily due to their significant biological activity and broad application prospects. Herein, we disclose a method for the construction from prochiral phosphinamides aryl iodides via palladium- chiral norbornene-catalyzed desymmetric annulation. were formed with scope excellent enantiomeric excesses. It is noteworthy that synthetic value this procedure was proven by variety transition metal-catalyzed cross-coupling reactions using C–Br bond on product versatile linchpin electrophile.

Language: Английский

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