Nickel-catalyzed decarbonylation of -acylated N-heteroarenes.

Chem Sci

Department of Applied Chemistry , Faculty of Engineering , Osaka University, Suita , Osaka 565-0871 , Japan . Email: ; Email:

Published: July 2019

Nickel-catalyzed decarbonylation of -acylated N-heteroarenes is developed. This method can be used to produce a variety of -aryl heteroarenes, including pyrroles, indoles, carbazoles and phenoxazines, using benzoic acid derivatives as arylating reagents. Arylnickelamide intermediates that are relevant to the catalytic reaction were characterized by X-ray crystallography. When -acylated benzimidazoles are used as substrates, decarbonylation accompanied 1,2-migration to form 2-arylated benzimidazoles.

Download full-text PDF

Source
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6625484PMC
http://dx.doi.org/10.1039/c9sc02035gDOI Listing

Publication Analysis

Top Keywords

nickel-catalyzed decarbonylation
8
decarbonylation -acylated
8
-acylated n-heteroarenes
8
n-heteroarenes nickel-catalyzed
4
n-heteroarenes developed
4
developed method
4
method produce
4
produce variety
4
variety -aryl
4
-aryl heteroarenes
4

Similar Publications

The myriad nickel-catalyzed cross-coupling reactions rely on the formation of an organonickel intermediate, but limitations in forming monoalkylnickel species have limited options for C(sp) cross-coupling. The formation of monoalkylnickel(II) species from abundant carboxylic acid esters would be valuable, but carboxylic acid derivatives are primarily decarboxylated to form alkyl radicals that lack the correct reactivity. In this work, we disclose a facile oxidative addition and decarbonylation sequence that forms monoalkylnickel(II) intermediates through a nonradical process.

View Article and Find Full Text PDF

Ligand Relay for Nickel-Catalyzed Decarbonylative Alkylation of Aroyl Chlorides.

Adv Sci (Weinh)

March 2024

School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, China.

Transition metal-catalyzed direct decarboxylative transformations of aromatic carboxylic acids usually require high temperatures, which limit the substrate's scope, especially for late-stage applications. The development of the selective decarbonylative of carboxylic acid derivatives, especially the most fundamental aroyl chlorides, with stable and cheap electrophiles under mild conditions is highly desirable and meaningful, but remains challenging. Herein, a strategy of nickel-catalyzed decarbonylative alkylation of aroyl chlorides via phosphine/nitrogen ligand relay is reported.

View Article and Find Full Text PDF

Effects of phosphine ligands in nickel-catalyzed decarbonylation reactions of lactone.

Org Biomol Chem

September 2023

Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou, Henan 450001, China.

Due to the ubiquity of carbonyl compounds and the abundance of nickel on the earth, nickel-catalyzed decarbonylation has garnered increasing attention in recent years. This type of reaction has seen significant developments in various aspects; however, certain challenges concerning reactivity, selectivity, and transformation efficiency remain pressing and demand urgent resolution. In this study, we employed DFT calculations to investigate the mechanism of nickel-catalyzed decarbonylation reactions involving lactones, as well as the effects of phosphine ligands.

View Article and Find Full Text PDF

Formal Cross-Coupling of Amines and Carboxylic Acids to Form sp-sp Carbon-Carbon Bonds.

J Am Chem Soc

May 2023

Department of Medicinal Chemistry, College of Pharmacy, University of Michigan, Ann Arbor, Michigan 48109, United States.

Amines and carboxylic acids are abundant synthetic building blocks that are classically united to form an amide bond. To access new pockets of chemical space, we are interested in the development of amine-acid coupling reactions that complement the amide coupling. In particular, the formation of carbon-carbon bonds by formal deamination and decarboxylation would be an impactful addition to the synthesis toolbox.

View Article and Find Full Text PDF

Nickel-Catalyzed Decarbonylative Reductive Alkylation of Aroyl Fluorides with Alkyl Bromides.

Org Lett

December 2022

Research Institute for Interdisciplinary Science, Okayama University, 3-1-1 Tsushimanaka, Kita-ku, Okayama 700-8530, Japan.

This paper describes the nickel-catalyzed reductive alkylation of aroyl fluorides with alkyl bromides in a decarbonylative manner. In this reaction, various functional groups are well tolerated and the C()-C() bond can be constructed directly without the use of organometallic reagents. The present reaction is a cross-electrophile coupling via the radical pathway, affording the corresponding alkylarenes in moderate to good yields.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!