Bifunctional Ligand Enables Gold‐Catalyzed Propargyl C‐H Functionalization via Reactive Gold Allenylidene Intermediate DOI

Yongliang Wei,

Jingxing Jiang, Yaru Jing

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(29)

Опубликована: Апрель 25, 2024

Abstract Gold allenylidene species have been seldom exploited as reactive intermediates in synthetically versatile catalytic reactions. By employing alkynylbenziodoxoles the substrates and bifunctional WangPhos metal ligand, this work demonstrated ready access to these of general substitution patterns their electrophilic reactivities at γ‐carbon center with a diverse range nucleophiles. The reaction is driven by reductive decomposition benziodoxole moiety achieves replacement propargylic proton an N/O/C‐based nucleophile, hence realizing reactivity umpolung. Corroborated Density Functional Theory (DFT) calculations, mechanism involves mild deprotonation. In contrast prior works tertiary amine functionality, weakly BrØnsted‐basic amide group surprisingly effective deprotonation position under gold‐ligand cooperation regime.

Язык: Английский

Fe(III)-Catalyzed Ring Expansion of Cyclopropenone from Olefins via Radicals to Access Pyrone and Indanone Derivatives DOI
Yao Xiao, Dongwei Huang,

Jie Liao

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 11, 2025

A novel approach for the synthesis of pyrone and indanone derivatives utilizing Fe(III)-catalyzed reductive radical ring expansion olefins cyclopropenone has been proposed. The preliminary mechanism study shows that alkyl is formed by hydrogen atom transfer, which can open tension then generate intermediate. There are two paths intermediate: when there a hydroxyl group at β-position olefin, reaction produces pyrones, otherwise 1-indanone generated. This method mild conditions wide substrate adaptability allows fragment to be conveniently accessed.

Язык: Английский

Процитировано

2
Bifunctional Ligand Enables Gold‐Catalyzed Propargyl C‐H Functionalization via Reactive Gold Allenylidene Intermediate DOI

Yongliang Wei,

Jingxing Jiang, Yaru Jing

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(29)

Опубликована: Апрель 25, 2024

Abstract Gold allenylidene species have been seldom exploited as reactive intermediates in synthetically versatile catalytic reactions. By employing alkynylbenziodoxoles the substrates and bifunctional WangPhos metal ligand, this work demonstrated ready access to these of general substitution patterns their electrophilic reactivities at γ‐carbon center with a diverse range nucleophiles. The reaction is driven by reductive decomposition benziodoxole moiety achieves replacement propargylic proton an N/O/C‐based nucleophile, hence realizing reactivity umpolung. Corroborated Density Functional Theory (DFT) calculations, mechanism involves mild deprotonation. In contrast prior works tertiary amine functionality, weakly BrØnsted‐basic amide group surprisingly effective deprotonation position under gold‐ligand cooperation regime.

Язык: Английский

Процитировано

5
NHC-Catalyzed and Brønsted Acid Copromoted E → Z Isomerization Mode of Breslow Intermediates Leading to Ralfuranones DOI

Qingyun Wang,

Xuyang Liang,

Mingyi Pan

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 12, 2025

Different Z/E-isomers of functional molecules display distinct chemical and biological activities. The E → Z isomerization reaction is a contra-thermodynamic direction presents long-standing challenge in synthetic transformation. To date, organic catalysis methods for manipulating E/Z are still under development. Here we show new N-heterocyclic carbene (NHC)-catalyzed mode. E-isomer enedial undergoes to give Z-isomer Breslow intermediate via NHC catalysis, an intramolecular hydrogen bond can greatly stabilize this conformation. Subsequently, the Brønsted acid promotes further redox-neutral reaction. desired ralfuranone products obtained from our method be readily transformed various molecules.

Язык: Английский

Процитировано

0
Bifunctional Ligand Enables Gold‐Catalyzed Propargyl C‐H Functionalization via Reactive Gold Allenylidene Intermediate DOI

Yongliang Wei,

Jingxing Jiang, Yaru Jing

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(29)

Опубликована: Апрель 25, 2024

Abstract Gold allenylidene species have been seldom exploited as reactive intermediates in synthetically versatile catalytic reactions. By employing alkynylbenziodoxoles the substrates and bifunctional WangPhos metal ligand, this work demonstrated ready access to these of general substitution patterns their electrophilic reactivities at γ‐carbon center with a diverse range nucleophiles. The reaction is driven by reductive decomposition benziodoxole moiety achieves replacement propargylic proton an N/O/C‐based nucleophile, hence realizing reactivity umpolung. Corroborated Density Functional Theory (DFT) calculations, mechanism involves mild deprotonation. In contrast prior works tertiary amine functionality, weakly BrØnsted‐basic amide group surprisingly effective deprotonation position under gold‐ligand cooperation regime.

Язык: Английский

Процитировано

0