Functionalization of Siloxanes with Arynes Generated from <i>o</i>-Triazenylarylboronic Acids

Chemical and Pharmaceutical Bulletin, Год журнала: 2024, Номер 72(5), С. 487 - 497

Опубликована: Май 20, 2024

Herein, we report the functionalization of polyhedral oligosilsesquioxanes (POSS) and related siloxanes with arynes. Using o-triazenylarylboronic acids as aryne precursors silica gel activator, transformation siloxane bearing various arynophilic moieties on side chains was achieved high yields without touching core. This method applied to conjugation POSS pharmaceutical cores using an derived from synthetic intermediate cabozantinib. Furthermore, orthogonal dual realized by combining reaction Huisgen cyclization.

Язык: Английский

Revisiting the Synthetic Utility of 4,5‐Dehydro[2.2]paracyclophane

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер unknown

Опубликована: Окт. 22, 2024

Abstract 4,5‐Dehydro[2.2]paracyclophane, an aryne species of [2.2]paracyclophane ([2.2]PCP) was reported more than half a century ago. However, despite its potential usefulness for preparing [2.2]PCP derivatives, this is rarely considered in synthetic applications, probably because the efficiency generation and reaction with arynophiles are low under harsh conditions classical methods involving precursors. We have prepared o ‐iodoaryl triflate‐ ‐silylaryl triflate‐type precursors achieved 4,5‐dehydro[2.2]PCP, which reacted diverse range to afford functionalized including [2.2]PCP‐fused π‐extended polyaromatics. Our results highlight utility historically overlooked 4,5‐dehydro[2.2]PCP intermediate.

Язык: Английский

Development of 3-triazenylaryne and its application to iterative aryne reactions via o-triazenylarylboronic acids

Chemical Communications, Год журнала: 2023, Номер 59(96), С. 14249 - 14252

Опубликована: Янв. 1, 2023

A novel aryne species 3-triazenylaryne has been developed as a divergent platform for the generation of 3-alkynylaryne through o -triazenylarylboronic acids.

Язык: Английский