An Annulative Synthetic Strategy for Building Triphenylene Frameworks by Multiple C−H Bond Activations

Abstract

C-H activation is a versatile tool for appending aryl groups to aromatic systems. However, heavy demands on multiple catalytic cycle operations and site-selectivity have limited its use for graphene segment synthesis. A Pd-catal- yzed one-step synthesis of functionalized triphenylene frameworks is disclosed, which proceeds by 2- or 4-fold C-H arylation of unactivated benzene derivatives. A Pd (dibenzylideneacetone) catalytic system, using cyclic diaryliodonium salts as π-extending agents, leads to site-selective inter- and intramolecular tandem arylation sequences. Moreover, N-substituted triphenylenes are applied to a field-effect transistor sensor for rapid, sensitive, and reversible alcohol vapor detection.

Rapid Access to Nanographenes and Fused Heteroaromatics by Palladium‐Catalyzed Annulative π‐Extension Reaction of Unfunctionalized Aromatics with Diiodobiaryls

“…Currently, various types of transformations are categorized as APEX reactions . Although many APEX reactions of heteroaromatics have been reported, the APEX reactions of inactive aromatic hydrocarbons such as benzenes, naphthalenes, and PAHs are still limited and thus regarded as challenging subjects . Development of new APEX chemistry for PAHs is highly demanded in the field of nanocarbon and material sciences.…”

Graphene chemiresistors modified with functionalized triphenylene for highly sensitive and selective detection of dimethyl methylphosphonate

“…The electrical properties of graphene can be manipulated without degrading its material properties. 18 The graphene sensor developed in this study exhibits a sensitivity of 1.3 ppm to DMMP, which is the highest of all graphene-based chemiresistors reported till date. In addition, its response to DMMP is two orders of magnitude higher than that to other volatile organic compounds, indicating high selectivity of the functionalized graphene sensor.…”

“…S1 †). 18 The functionalized triphenylenes are stable and can thus be handled in air. A monolayer graphene was synthesized by chemical vapor deposition (CVD) on a copper foil, and transferred onto a silicon substrate with thermal oxides, using the poly(methyl methacrylate) (PMMA)-mediated transfer method.…”

“…In this study, we functionalize graphene with N-substituted triphenylenes obtained by palladium-catalyzed one-step synthesis 18 to detect DMMP with high sensitivity and selectivity. The functionalized triphenylenes are easily soluble, processable, and applicable to graphene-based chemiresistive gas sensors.…”

Atom‐Economical Applications of Diaryliodonium Salts

“…In 2017, the Hong group explored palladium‐catalyzed two‐fold C−H bond activations by using symmetric cyclic diaryliodonium salts as the arylation agents for the construction of functionalized triphenylene frameworks (Scheme ) . Amide moieties were chosen as the directing groups owing to their wide application in natural products and organic materials.…”