Arynes are important synthetic intermediates that are usually generated under alkaline conditions. We developed a method for generating arynes using two hydroxy compounds as activators. -Triazenylarylboronic acids generate (hetero)arynes when activated by a combination of ethylene glycol, pinacol, and -nitrophenol; these arynes then react with a range of arynophiles under slightly acidic conditions that complement the conventional basic conditions with unique chemoselectivities observed even in the presence of excess hydroxy compounds.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.joc.4c02946 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Aryne Generation from -Triazenylarylboronic Acids Induced by 1,2-Diols and 4-Nitrophenol.
J Org Chem
January 2025
Meiji Pharmaceutical University, 2-522-1 Noshio, Kiyose, Tokyo 204-8588, Japan.
Arynes are important synthetic intermediates that are usually generated under alkaline conditions. We developed a method for generating arynes using two hydroxy compounds as activators. -Triazenylarylboronic acids generate (hetero)arynes when activated by a combination of ethylene glycol, pinacol, and -nitrophenol; these arynes then react with a range of arynophiles under slightly acidic conditions that complement the conventional basic conditions with unique chemoselectivities observed even in the presence of excess hydroxy compounds.
View Article and Find Full Text PDFHerein, we report the functionalization of polyhedral oligosilsesquioxanes (POSS) and related siloxanes with arynes. Using o-triazenylarylboronic acids as aryne precursors and silica gel as the activator, the transformation of siloxane bearing various arynophilic moieties on the side chains was achieved with high yields without touching the siloxane core. This method was applied to the conjugation of POSS and pharmaceutical cores using an aryne derived from the synthetic intermediate of cabozantinib.
View Article and Find Full Text PDFDevelopment of 3-triazenylaryne and its application to iterative aryne reactions -triazenylarylboronic acids.
Chem Commun (Camb)
November 2023
Meiji Pharmaceutical University, 2-522-1 Noshio Kiyose, Tokyo 204-8588, Japan.
Herein, a novel aryne species, 3-triazenylaryne, was developed and its regioselectivity was revealed. Based on the regioselectivity, various alkyne moieties were introduced by iodoalkynylation, and further derivatization to -triazenylarylboronic acids as 3-alkynylaryne precursors was enabled. Therefore, 3-triazenylaryne was developed as a divergent platform for the generation of various 3-alkynylarynes.
View Article and Find Full Text PDFWe report aryne generation from 2-triazenylarylboronic acids using an activator such as Brønsted acids, Lewis acids, and solid acids. With the use of (±)-Camphorsulfonic acid [(±)-CSA], the aryne precursors provided cycloadducts with a range of arynophiles in high yields. Aryne generated under the acidic conditions underwent chemoselective cycloaddition with a furan in the presence of a basic arynophile, namely an amine.
View Article and Find Full Text PDFWant 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!