Single Step Synthesis of Non-symmetric Azoarenes Using Buchwald–Hartwig Amination DOI Creative Commons
Martin Kocúrik,

Pavlína Konopáčová,

Lukáš Kolman

et al.

ACS Omega, Journal Year: 2024, Volume and Issue: 9(47), P. 47105 - 47113

Published: Nov. 15, 2024

Aromatic azo compounds stand as a highly sought-after class of substances owing to their extensive array applications across various fields. Despite significance, synthesis often presents challenges, requiring either multistep reactions or being restricted specific substrate types. In this study, we are showing the universality and mechanistic aspects one-step approach for nonsymmetrical azoarenes via Buchwald–Hartwig amination reaction (pseudo)haloaromatics with arylhydrazines, conducted in presence atmospheric oxygen. This protocol yields products up 85% yield is compatible wide substituents, making it adaptable. Notably, inclusion BINAP ligand plays pivotal role achieving favorable outcomes. study not only offers versatile solution long-standing synthetic challenge but also provides experimental computational insights into mechanisms driving reaction.

Language: Английский

Reductive C(sp2)–Si Cross‐Couplings by Catalytic Sodium‐Bromine Exchange DOI Creative Commons
Baptiste Neil,

Thomas Déis,

Louis Fensterbank

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 29, 2024

Abstract The metal‐halogen exchange reaction constitutes one of the most important preparative routes towards polar organometallic reagents such as aryllithium or Grignard reagents. However, despite extensive developments over past eight decades, this fundamental elementary step has only been exploited stoichiometrically. Against background, we demonstrate that sodium‐bromine can be implemented in a catalytic setting mean to activate C(sp 2 )−Br bonds transition metal‐free manner en route regioselective and general preparation (hetero)aryl silanes. Simply treating structurally diverse bromides with N ‐ tert ‐butyl‐ N’ ‐silyldiazenes ( t Bu−N=N− Si ) silylating inexpensive sodium alkoxides promoters yields range aromatic organosilicon compounds under ambient conditions. Mechanistic studies provide solid evidence for involvement ‐butyl metalating agent.

Language: Английский

Citations

1
Reductive C(sp2)–Si Cross‐Couplings by Catalytic Sodium‐Bromine Exchange DOI Creative Commons
Baptiste Neil,

Thomas Déis,

Louis Fensterbank

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 29, 2024

Abstract The metal‐halogen exchange reaction constitutes one of the most important preparative routes towards polar organometallic reagents such as aryllithium or Grignard reagents. However, despite extensive developments over past eight decades, this fundamental elementary step has only been exploited stoichiometrically. Against background, we demonstrate that sodium‐bromine can be implemented in a catalytic setting mean to activate C(sp 2 )−Br bonds transition metal‐free manner en route regioselective and general preparation (hetero)aryl silanes. Simply treating structurally diverse bromides with N ‐ tert ‐butyl‐ N’ ‐silyldiazenes ( t Bu−N=N− Si ) silylating inexpensive sodium alkoxides promoters yields range aromatic organosilicon compounds under ambient conditions. Mechanistic studies provide solid evidence for involvement ‐butyl metalating agent.

Language: Английский

Citations

0
Single Step Synthesis of Non-symmetric Azoarenes Using Buchwald–Hartwig Amination DOI Creative Commons
Martin Kocúrik,

Pavlína Konopáčová,

Lukáš Kolman

et al.

ACS Omega, Journal Year: 2024, Volume and Issue: 9(47), P. 47105 - 47113

Published: Nov. 15, 2024

Aromatic azo compounds stand as a highly sought-after class of substances owing to their extensive array applications across various fields. Despite significance, synthesis often presents challenges, requiring either multistep reactions or being restricted specific substrate types. In this study, we are showing the universality and mechanistic aspects one-step approach for nonsymmetrical azoarenes via Buchwald–Hartwig amination reaction (pseudo)haloaromatics with arylhydrazines, conducted in presence atmospheric oxygen. This protocol yields products up 85% yield is compatible wide substituents, making it adaptable. Notably, inclusion BINAP ligand plays pivotal role achieving favorable outcomes. study not only offers versatile solution long-standing synthetic challenge but also provides experimental computational insights into mechanisms driving reaction.

Language: Английский

Citations

0