Alternating oligo(o,p-phenylenes) via ruthenium catalyzed diol–diene benzannulation: orthogonality to cross-coupling enables de novo nanographene and PAH construction

Abstract

Ruthenium(0) catalyzed diol–diene benzannulation enables formation of p-bromo-terminated alternating oligo(o,p-phenylenes) and, therefrom, diverse PAH materials.

Synthetic Applications of Oxidative Aromatic Coupling—From Biphenols to Nanographenes

“…[135] Roberts,K rische,a nd co-workers have exploited ruthenium-catalyzed diol-diene benzannulation for the construction of various polyphenylene-type PA Hprecursors. [137] Treatment of zigzag-type oligophenylene precursors with FeCl 3 in dichloromethane in the presence of 4 molecular sieves led to the formation of nine new C aryl -C aryl bonds and afforded PA Hs 149 a-d in moderate yields (9-40 %; Figure 10). The presence of nitrogen bridges in 149 d significantly decreased the reaction efficiency.…”

Synthesis and Photophysical Properties of Soluble N‐Doped Rubicenes via Ruthenium‐Catalyzed Transfer Hydrogenative Benzannulation

“…In the course of developing transfer hydrogenative C−C couplings, [8] ruthenium‐catalyzed [4+2] cycloadditions of vicinal diols, ketols, or diketones with dienes, [9] 1,6‐diynes [10] and other π‐unsaturated partners [11] were developed in our laboratory [12] . The diol‐containing cycloadducts readily undergo dehydration (or deoxydehydration) to form aromatic rings, unlocking a new benzannulation strategy that has opened novel synthetic routes to acenes, [13a] oligo(phenylene) cages, [13b,c] nanographenes, [13d] and diindenoperylenes [13e] . Herein, we describe a fundamentally new strategy for the construction of highly soluble rubicene derivatives based on ruthenium‐catalyzed diketone‐butadiene benzannulation (Figure 1), which has resulted in the first synthesis of 3,10‐(di‐ tert ‐butyl)rubicene and a suite of N‐doped congeners, as well as preliminary studies on their photophysical properties and electronic states.…”

Syntheseanwendungen der oxidativen aromatischen Kupplung – von Biphenolen zu Nanographenen

“…Roberts, Krische et al. haben die Ruthenium‐katalysierte Diol‐Dien‐Benzanellierung für den Aufbau verschiedener PAK‐Vorläufer vom Polyphenylentyp genutzt . Die Umsetzung von Oligophenylenvorläufern vom Zickzacktyp mit FeCl 3 in Dichlormethan in Gegenwart von 4‐Å‐Molekularsieb führte zur Bildung von neun neuen C Aryl ‐C Aryl ‐Bindungen und lieferte PAKs 149 a – d in moderaten Ausbeuten (9–40 %; Abbildung ).…”