Catalytic C H activation-initiated transdiannulation: An oxygen transfer route to ring-fluorinated tricyclic γ-lactones

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: 35(9), P. 109494 - 109494

Published: Jan. 6, 2024

Language: Английский

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Catalyst-controlled directing group translocation in the site selective C–H functionalization of 3-carboxamide indoles and metallocarbenes

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

Published: Jan. 2, 2025

Complementary methods toward the selective functionalization of indole and oxindole frameworks employing an alternative strategy in heteroaryl C–H functionalizations are presented herein. This work focuses on a catalyst-controlled, site activation/functionalization 3-acyl indoles, wherein amide serves as robust versatile directing group capable undergoing concomitant 1,2-acyl translocation/C–H presence RhI/AgI co-catalysts to provide cross-coupled adducts high yields. In contrast, use IrIII/AgI catalysts subverted migration afford corresponding C2-functionalized products good excellent A notable feature catalyst systems was exceptional level selectivity observed which functionalized indoles were obtained exclusively. Mechanistic experiments indicate concerted step metallation occurring through electrophilic aromatic substitution process. Here, authors present divergent, transition metal catalyst-controlled 3-carboxamide indoles. One set conditions enables 2-position, while other translocation carboxamide at 3-position.

Language: Английский

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Imine induced metal-free C–H arylation of indoles

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(24), P. 6063 - 6069

Published: Jan. 1, 2023

A simple, mild, and metal- extra-auxiliary group-free method for the direct arylation of indole-3-carbaldehydes induced by an in situ generated transient directing group was developed.

Language: Английский

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Engineering Saccharomyces cerevisiae for the de novo Production of Halogenated Tryptophan and Tryptamine Derivatives

ChemistryOpen, Journal Year: 2023, Volume and Issue: 12(4)

Published: March 16, 2023

Abstract The indole scaffold is a recurring structure in multiple bioactive heterocycles and natural products. Substituted indoles like the amino acid tryptophan serve as precursor for wide range of products with pharmaceutical or agrochemical applications. Inspired by versatility these compounds, medicinal chemists have decades exploited core drug discovery process. With aim tuning properties lead candidates, regioselective halogenation common strategy. However, chemical generally expensive, has poor atom economy, lacks regioselectivity, generates hazardous waste streams. As an alternative, this work we engineer industrial workhorse Saccharomyces cerevisiae de novo production halogenated tryptamine derivatives. Functional expression bacterial halogenases together partner flavin reductase decarboxylase resulted chlorine bromine. Furthermore, combining halogenases, di‐halogenated molecules was also achieved. Overall, works paves road new‐to‐nature yeast.

Language: Английский

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Cobalt(II)-Catalyzed Selective C2–H Heck Reaction of Native (N–H) Indoles Enabled by Salicylaldehyde Ligand

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

Published: Jan. 8, 2025

Direct functionalization of native (N–H) indoles via C–H activation remains a challenge. Herein, we report salicylaldehyde-promoted cobalt-catalyzed selective C2–H Heck reaction with both active and unactivated olefins in the presence free N–H bonds. A series structurally diverse C2-alkenylated including natural product drug derivatives were prepared directly effectively without additional preprotection deprotection procedures.

Language: Английский

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Pd/NBE-Catalyzed One-Pot Modular Synthesis of Tetrahydro-γ-carbolines

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

Published: April 14, 2025

Tetrahydro-γ-carbolines are especially outstanding fused heterocyclic ring systems possessing significant biological activities in the central nervous system. Here, using commercially available NBE derivatives (NBEs), we report an efficient protocol for one-pot modular synthesis of 4-substituted tetrahydro-γ-carbolines via Catellani/aza-Michael addition cascade from easily 3-iodo-1-tosyl-1H-indole, aziridines and olefins. This approach exhibits a wide substrate scope, good yields, scalability, potential extension toward Mebhydroline analogues.

Language: Английский

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Boron-Catalyzed Formylation of Indoles Using Trimethyl Orthoformate as Carbonyl Source

ACS Omega, Journal Year: 2025, Volume and Issue: 10(20), P. 20497 - 20508

Published: May 14, 2025

This study presents a practical, efficient, and scalable approach for the C-H formylation of indoles their derivatives using alkyl orthoesters as formylating agents. Boron trifluoride diethyl etherate (BF3·OEt2) was found to be an effective stoichiometric catalyst, with trimethyl orthoformate (TMOF) acting reliable formyl source. method enables rapid efficient synthesis wide range C-formylindoles, including C3, C2, C6, C7 derivatives, well electron-rich aromatic carbaldehydes. Key advantages protocol include its operational simplicity, use inexpensive readily available reagents, neat conditions, ambient reaction temperatures, short times (typically 1-5 min), broad substrate tolerance, scalability. These features make highly versatile suitable diverse synthetic applications.

Language: Английский

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Acetoxy Group-Directed Regioselective C2 Alkenylation of Indoles via Pd–Ag Bimetallic Catalysis

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(20), P. 14423 - 14434

Published: Oct. 5, 2023

Regioselective C–H functionalizations of indoles reported to date with directing groups at C3 mainly rely on functional that are linked the indole via C–C bonds. However, core by C–X linkages also attractive due possibility further modifications bond. Herein, we report a 3-acetoxy group for regioselective C2 alkenylation activation-based, cross-dehydrogenative, oxidative Heck-type reaction. The reaction is catalyzed Pd(II) and Ag(I) stoichiometric Cu(II) as oxidant provides 2-alkenylated in yields 52–84%. conditions compatible several different positions well N-protecting or free NH core. With respect alkene coupling partners, reactions successful acrylates, vinyl sulfates, phosphates. Specifically designed experiments, density theory (DFT) computational studies, reveal heterodinuclear [Pd(μ-OAc)3Ag] bimetallic species actual catalyst responsible alkenylation. A mechanistic path involving this catalytic was found be favorable over other possible pathways explaining observed regioselectivity through DFT studies.

Language: Английский

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Directed Regioselective Arylation of Imidazo[1,2-a]pyridine-3-carboxamides using Rh(III) catalysis.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(35), P. 7121 - 7127

Published: Jan. 1, 2024

We introduced, for the first time, N -methoxyamide directed proximal C–H bond activation of imidazo[1,2- a ]pyridines C(sp 2 )–C(sp ) formation via transition metal catalysed approach to obtain C-5 arylated ]pyridines.

Language: Английский

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A Metal-Free Direct Decarboxylative Fluoroacylation of Indole Carboxylic Acids with Fluorinated Acids

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 25, 2024

A straightforward preparation of diversified fluorinated indol-3-yl ketones was developed by the direct decarboxylative fluoroacylation indole carboxylic acids. The reaction could be performed on a gram scale under net conditions. Neither metal catalyst nor an additive employed. This methodology featured simple conditions, high efficiency, exclusive selectivity, broad substrate scope, and easy operation, which allowed it to meet green chemistry requirement modern pharmaceutical industry. Control experiments confirmed that radical process might involved in tandem sequence.

Language: Английский

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