Video Experimental Relacionado

Updated: Aug 16, 2025

A Direct, Regioselective and Atom-Economical Synthesis of 3-Aroyl-N-hydroxy-5-nitroindoles by Cycloaddition of 4-Nitronitrosobenzene with Alkynones

A Direct, Regioselective and Atom-Economical Synthesis of 3-Aroyl-N-hydroxy-5-nitroindoles by Cycloaddition of 4-Nitronitrosobenzene with Alkynones

Published on: January 21, 2020

Tandem C/N-Difuncionalización de nitroarenos: Aminación reductora y anulación por una secuencia de expansión y

Gen Li¹, Marissa N Lavagnino¹, Siraj Z Ali¹

¹Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.

Journal of the American Chemical Society

|December 23, 2022

Resumen

Un nuevo método sintético transforma los nitroarenos en valiosos productos ortoaminados. Este proceso catalizado por el organofosforo genera nitrenos de arilo, lo que conduce a las azepinas desaromatizadas y, en última instancia, a las anilidas y los benzimidazoles.

Área de la Ciencia:

Química orgánica
Metodología sintética
Catálisis

Sus antecedentes:

Las transformaciones del nitroareno son cruciales en la síntesis orgánica.
El desarrollo de métodos eficientes para la ortofuncionalización sigue siendo un desafío.
El acceso a los heterociclos complejos que contienen nitrógeno requiere estrategias innovadoras.

Objetivo del estudio:

Informar sobre un nuevo método sintético para la transformación reductiva de los nitroarenos.
Para lograr la ortoaminación y la anulación de los sistemas aromáticos.
Para sintetizar el 2-aminoanilido y los derivados del benzimidazol.

Principales métodos:

Desoxigenación exhaustiva de los nitroarenos mediante el uso de un catalizador organofosforado y un suave reductor.
Generación y captura de nitrenos de arilo.
La expansión del anillo para formar 2-amino-3H-azepinas desaromatizadas.
Tratamiento de electrófilo acilo seguido de electrociclado 6π y funcionalización C-H.

Principales resultados:

El método desarrollado transforma con éxito los nitroarenos en productos ortoaminados y anulados.
Los nitrenos de arilo se generan y posteriormente son atrapados por nucleófilos de aminas.
Las 2-amino-3H-azepinas aromatizadas se forman como intermediarios clave.
El proceso produce productos de 2-aminoanilida y benzimidazol a través de la funcionalización C-H.

Conclusiones:

Se ha establecido una vía sintética versátil para acceder a compuestos aromáticos ortofuncionalizados.
El método proporciona una nueva vía para valiosos andamios de 2-aminoanilida y benzimidazol.
Este trabajo expande la utilidad sintética de los nitroarenos en la química orgánica.

Más Videos Relacionados

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

Published on: January 19, 2016

Preparation of Contiguous Bisaziridines for Regioselective Ring-Opening Reactions

Preparation of Contiguous Bisaziridines for Regioselective Ring-Opening Reactions

Published on: July 28, 2022

Videos de Conceptos Relacionados

Preparation of Amines: Reductive Amination of Aldehydes and Ketones

Preparation of Amines: Reductive Amination of Aldehydes and Ketones

Carbonyl compounds and primary amines undergo reductive amination first to produce imines, followed by secondary amines in the same reaction mixture, using selective reducing agents like sodium cyanoborohydride or sodium triacetoxyborohydride. Reductive amination produces different degrees of substitution of amines depending on the starting amine substrate.

Electrophilic Aromatic Substitution: Nitration of Benzene

Electrophilic Aromatic Substitution: Nitration of Benzene

The nitration of benzene is an example of an electrophilic aromatic substitution reaction. It involves the formation of a very powerful electrophile, the nitronium ion, which is linear in shape. The reaction occurs through the interaction of two strong acids, sulfuric and nitric acid.

Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation

Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation

Robinson annulation is a base-catalyzed reaction for the synthesis of 2-cyclohexenone derivatives from 1,3-dicarbonyl donors (such as cyclic diketones, β-ketoesters, or β-diketones) and α,β-unsaturated carbonyl acceptors. Named after Sir Robert Robinson, who discovered it, this reaction yields a six-membered ring with three new C–C bonds (two σ bonds and one π bond).

Preparation of Nitriles

Preparation of Nitriles

One of the common methods to prepare nitriles is the dehydration of amides. This method requires strong dehydrating agents like phosphorous pentoxide or boiling acetic anhydride for converting amides to nitriles. Another reagent namely, thionyl chloride also accomplishes the dehydration of amides, where amide acts as a nucleophile. The first step of the mechanism involves the nucleophilic attack by the amide on the thionyl chloride to form an intermediate. In the next step, the electron pairs...

Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions

Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions

Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...

Preparation of Amines: Reduction of Amides and Nitriles

Preparation of Amines: Reduction of Amides and Nitriles

Nitriles can be reduced to primary amines using reducing agents like lithium aluminum hydride or catalytic hydrogenation. The reduction introduces an amino group with an extra carbon in the skeleton. Nitriles are formed from the reaction between alkyl halides and sodium cyanide through the SN2 mechanism. Primary alkyl halides are the preferred substrates to prepare nitriles.
Amides can be reduced to primary, secondary, and tertiary amines using catalytic hydrogenation, active metals like Fe,...