Annulative π-Extension of Unactivated Benzene Derivatives through Nondirected C–H Arylation

Abstract

Annulative π-extension chemistry provides a concise synthetic route to polycyclic arenes. Herein, we disclose a nondirected annulation approach of unactivated simple arenes. The palladium-catalyzed 2-fold C–H arylation event facilitates tandem C–C linkage relays to furnish fully benzenoid triphenylene frameworks using cyclic diaryliodonium salts. The inseparable regioisomeric mixture of 1- and 2-methyltriphenylenes is identified by the combined analysis of ion mobility-mass spectrometry, gas-phase infrared spectroscopy, and molecular simulation studies.

Rapid access to polycyclic N-heteroarenes from unactivated, simple azines via a base-promoted Minisci-type annulation

“…In base-promoted homolytic aromatic substitution (BHAS) or unimolecular radical nucleophilic substitution (S RN 1) reactions, aryl radicals are generated by single-electron transfer (SET) from organic electron donors (OEDs) to aryl halides. As π-extension agents, cyclic diaryliodonium salts 21 , 22 and dibenzosilole derivatives 23 have been successfully applied in both directed and nondirected C–H annulations (Fig. 2a ).…”

“…to provide a pathway for OED formation ( vide infra ). Notably, products 30 and 31 were inaccessible through direct C–H arylation reactions 22 . APEX reactions to access well-defined PACs or N-PACs typically have low-to-moderate yields because they (i) employ unfunctionalized substrates and (ii) involve twofold C–C bond formation via C–H functionalization.…”

An Evaluation of Useful Daylight Illuminance in an Office Room with a Light Shelf and Translucent Ceiling at 51° N

“…• use of a diffusion sheet [26] • evaluation of a light shelf based on energy consumption [27] • light shelf with a solar module [28] • light shelf based on reflector curvature [29] • application of a prism sheet [30] • movable light shelf with a rolling reflector [31] • light shelves with photovoltaic modules [32] Avila-Zamora and Murillo-Quirós experiment • three different anidolic systems were evaluated (anidolic ceiling, integrated anidolic system, anidolic solar blinds)…”

“…In the following years till the current time, the team of Prof. Heangwoo Lee published 11 papers considering different aspects of a light shelf and its performance. Those papers feature a light shelf using diffused reflection [22]; a movable light shelf system [23]; an awning system with a built-in light shelf [24]; the use of a diffusion sheet [25]; an evaluation of a light shelf based on energy consumption [26]; a light shelf with a solar module [27]; a light shelf based on reflector curvature [28] application of a prism sheet [29]; a movable light shelf with a rolling reflector [30]; and finally, in 2021, light shelves with photovoltaic modules [31].…”

Small organic molecules with tailored structures: initiators in the transition-metal-free C–H arylation of unactivated arenes

“…Moreover, DFT calculations gave specic information about the mechanism (Scheme 1g). 35 Prompted by the aforementioned and other related literature reports, [36][37][38][39][40][41][42][43] herein, we propose a catalytic system composed of a small organic molecule ((2-(methylamino)phenyl)methanol, abbreviated as SOM in this article) and a strong base ( t BuOK) for the synthesis of biphenyl and its derivatives (good to excellent yields, broad substrate scope and good functional group tolerance) from arenes and aryl iodides at 100 C via a single electron transfer (SET) process. The catalytically active molecule with a specically tailored structure was designed and could be applied to scale-up experiments, showing potential for industrial production.…”