Rules of Nucleophilic Additions to Zigzag Nanographene Diones**

Abstract

Nucleophilic addition of carbon-centered nucleophiles to nanographene ketones represents avaluable late-stage method for the functionalization of zigzag nanographenes,but its use is rare in the chemical literature.U sing two model systems,non-KekulØ triangulene-4,8-dione and KekulØ anthanthrone,w ei dentify unexpected regioselectivities and uncover the rules that govern these reactions.C onsidering the large number of nanographene ketones that have been reported since the pioneering work of Eric Clar,this method enables synthesis and exploration of hitherto unknown functionalizedn anographenes.

Synthesis and Isolation of a Kinetically Stabilized Crystalline Triangulene

“…The introduction of mesityl groups to the carbonyl carbons of 3 was then examined. The use of mesityllithium as the nucleophile did not produce the desired addition product 4 due to the nucleophilic attack at the α-carbon in a 1,4-addition manner . This undesired side reaction was effectively suppressed by employing mesityllithium in combination with either CeCl 3 or LaCl 3 ·2LiCl, , and we found that the use of LaCl 3 ·2LiCl was more operationally simple and reproducible.…”

“…The use of mesityllithium as the nucleophile did not produce the desired addition product 4 due to the nucleophilic attack at the α-carbon in a 1,4-addition manner. 25 This undesired side reaction was effectively suppressed by employing mesityllithium in combination with either CeCl 3 26 or LaCl 3 •2LiCl, 27,28 and we found that the use of LaCl 3 •2LiCl was more operationally simple and reproducible. Demethylation and dehydration of 4 using trifluoroacetic acid proceeded with the concomitant migration of a hydroxy group to give 5 in 80% yield over two steps from 3.…”

The taming of Clar's hydrocarbon

“…The first attempt towards this goal was reported by Juríček et al in 2021. 53 In this approach ( Scheme 6 ), the first substituent in the center of one edge was installed by means of the Suzuki cross-coupling reaction of 3,5-di- tert -butylphenylboronic acid and TOT triflate. The resulting monosubstituted triangulene-4,8-dione displays a significantly improved solubility compared to the unsubstituted dione, which is practically insoluble.…”

Cost‐Effective Vat Orange 3‐Derived Organic Cathodes for Electrochemical Energy Storage

“…The 4,10-diphenyl substituted anthanthrone (Ph-AT) was prepared by Suzuki coupling of VO3 with phenylboronic acid in a yield of 87 %. [50,51] Polymer PAT-Ph was synthesized in a similar way as Ph-AT by using the bifunctional 1,4-phenylenebisboronic acid instead. Notably, all synthetic processes are simple, scalable, and merely use inexpensive chemical feedstocks.…”