Intermolecular amination of Ethyl Benzo ylacetate via photocatalytic nitrene transfer reactions

Organic Chemistry Frontiers, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This study reports a photocatalytic nitrene transfer reaction of 1,3-dicarbonyl. A broad range substrates and iodinanes are shown, enabling direct C–H functionalization without the need for pre-formed nucleophilic enolate equivalents.

Язык: Английский

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Acylsilanes as Weakly Coordinating Directing Groups for Metal-Catalyzed C–H Functionalization

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 6881 - 6894

Опубликована: Апрель 14, 2025

Язык: Английский

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Planar Chiral Rhodium Complex Based on the Tetrahydrofluorenyl Core for Enantioselective Catalysis

Organic Letters, Год журнала: 2023, Номер 25(49), С. 8906 - 8911

Опубликована: Дек. 5, 2023

A simple four-step route to a chiral tetrahydrofluorenyl rhodium catalyst from naturally occurring (−)-α-pinene was developed. Our approach does not use multistep and time-consuming procedures such as HPLC or diastereomeric resolution. The key success lies in the face-selective coordination of sterically hindered ligand, giving only one complex. This proved be highly efficient for asymmetric C–H annulation aryl hydroxamates with alkenes (yield up 95%, 91% ee) at low loading (up 0.4 mol % based on Rh).

Язык: Английский

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Tetrahydrofluorenyl rhodium complexes: positive impact of p-methoxybenzyl substituent on catalytic annulation reactions

Mendeleev Communications, Год журнала: 2024, Номер 34(1), С. 57 - 60

Опубликована: Янв. 1, 2024

Язык: Английский

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Acylsilanes in Transition-Metal-Catalyzed and Photochemical Reactions: Clarifying Product Formation

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(19), С. 14205 - 14209

Опубликована: Сен. 22, 2023

Acylsilanes are able to react as nucleophilic carbene precursors, electrophiles, and directing groups in C–H functionalization. To date, some of the products reportedly formed during transition-metal-catalyzed photochemical reactions involving acylsilanes have been incorrectly assigned. provide clarity, we herein address these structural misassignments detail revised structures. New insights into reactivity were also afforded via discovery that light-induced siloxy carbenes participate intramolecular 1,2-carbonyl addition proximal esters.

Язык: Английский

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Photoinduced Group Transposition via Iridium‐Nitrenoid Leading to Amidative Inner‐Sphere Aryl Migration

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(36)

Опубликована: Июнь 14, 2024

We herein report a fundamental mechanistic investigation into photochemical metal-nitrenoid generation and inner-sphere transposition reactivity using organometallic photoprecursors. By designing Cp*Ir(hydroxamate)(Ar) complexes, we induced photo-initiated ligand activation, allowing us to explore the amidative σ(Ir-aryl) migration reactivity. A combination of experimental studies, femtosecond transient absorption spectroscopy, density functional theory (DFT) calculations revealed that metal-to-ligand charge transfer enables σ(N-O) cleavage, followed by Ir-acylnitrenoid generation. The final group results in net transposition.

Язык: Английский

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Cu(I)-Catalyzed Highly Regioselective C–H Amidation of Quinoline N-Oxides with Dioxazolones

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Сен. 30, 2024

A Cu(I)-catalyzed highly regioselective synthesis of 2-acetamidequinoline

Язык: Английский

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Benzocyclobutenone Synthesis Exploiting Acylsilanes as Photofunctional Directing Groups

Chemical Science, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

The visible-light irradiation of acylsilane tethered vinyl ketones promotes an intramolecular Stetter-type reaction

Язык: Английский

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Photo-Induced Electrophilic Aromatic Substitution of Ferric Acyl Nitrene

Synthesis, Год журнала: 2023, Номер 56(03), С. 496 - 506

Опубликована: Сен. 27, 2023

Abstract A photo-induced intramolecular electrophilic aromatic substitution (SEAr) of N-acyloxyamides using FeCl3 in 1,4-dioxane is reported for the synthesis biologically interesting benzoxazin-3(4H)-ones. It believed that irradiation with a blue LED facilitates reaction, serving as source energy. The SEAr reaction pathway ascribed to electronic effects present aryl ring substrates. also applicable useful scaffolds possessing quinolin-2-one core, such an anticancer reagent and analogues brexipiprazole cilostamide.

Язык: Английский

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Synthesis of phosphine‐tethered indenyl ruthenium complexes through c‐h bonds activation followed by C‐C bond coupling: High performance catalysts for the redox isomerization of allylic alcohols

Applied Organometallic Chemistry, Год журнала: 2024, Номер 38(5)

Опубликована: Март 4, 2024

Reactions of 3‐(2‐pyridyl)indene and 5‐methyl‐3‐(2‐pyridyl)indene with Ru(PPh 3 ) Cl 2 , generated two phosphine‐tethered indenyl ruthenium complexes { η 5 κ 1 P ‐(C H 4 N‐C 9 R‐C 6 PPh )}RuCl(PPh (R = H, ; R CH ), respectively. While treatment 3‐(6‐methyl‐2‐pyridyl)indene gave a product ‐(CH C ( ); could further react NaBAr F to produce cationic complex [{ ‐C )}Ru(PPh )][BAr ] 15 ). When treated NaOMe in methanol, was converted into )}RuH(PPh )] 16 These five were investigated as catalysts for redox isomerization allylic alcohols, exhibited best catalytic activity the presence t BuOK, reaching quantitative yield min when α‐vinylbenzyl alcohol used substrate, requiring catalyst loading mol%.

Язык: Английский

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