Highly Regioselective Domino Benzannulation Reaction of Buta‐1,3‐diynes To Construct Irregular Nanographenes

Abstract

The properties of nanographenes can be tuned by changing their shapes, therefore the development of new methods suitable for the synthesis of various nanographenes is highly desirable. Described herein is an intramolecular InCl /AgNTf -catalyzed regioselective domino benzannulation reaction of buta-1,3-diynes to build irregular nanographenes. Different nanographene compounds were easily obtained in moderate to high yields through careful design of the precursor compounds. This new domino reaction was successfully applied to a fourfold alkyne benzannulation of dimethoxy-1,1'-binaphthalene derivatives to arrive at novel chiral butterfly ligand precursors. The regioselectivity of the benzannulation reaction was unambiguously confirmed by X-ray crystallography. Moreover, this new method enables us to synthesize different nanographene isomers and study their optical properties as a function of shape.

Emerging Bottom‐Up Strategies for the Synthesis of Graphene Nanoribbons and Related Structures

“…Interestingly,C halifoux and co-workers pushed the benzannulation concept further and reported ar egioselective domino benzannulation reaction of various 1,3-butadiyne derivatives (12)f or the preparation of PA Hs (13 a-f,Scheme 2). [67] This concept has yet to be tested for the synthesis of GNRs.…”

Synthesis, Structure, Photophysical Properties, and Photostability of Benzodipyrenes

“…Unlike our previous work on the synthesis of peropyrenes and teropyrenes through an InCl 3 ‐catalyzed multifold alkyne benzannulation, InCl 3 itself failed to fully cyclize 3 to 4 . Recently, we reported a domino benzannulation reaction of buta‐1,3‐diynes to construct irregular nanographenes, in which the InCl 3 ‐AgNTf 2 catalyst system was used . Upon treating compound 3 with this system in toluene at 100 °C for 24 hours, the BDP products 4 a and 4 b were isolated in 66 and 61 % yields, respectively.…”

Rhodium‐Catalyzed Copper‐Assisted Intermolecular Domino C−H Annulation of 1,3‐Diynes with Picolinamides: Access to Pentacyclic π‐Extended Systems

“…Although in these transformations each π system of the diyne undergoes migratory insertion independently of the other, we questioned whether an alternative mechanism would be possible in which the 1,3‐diyne could engage both alkyne motifs in an orchestrated sequence of insertion events, thereby enabling the access to new polycyclic aromatic architectures. During the final stages of our investigations, Chalifoux and co‐workers reported the first realization of this goal, namely the domino benzannulation reaction of 1,3‐diynes . In their elegant protocol, π expansion is achieved by an intramolecular double 6‐ endo‐dig cyclization of properly designed diaryl‐1,3‐butadiynes in the presence of InCl 3 /AgNTf 2 as catalyst (Scheme A).…”