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

Wataru Matsuoka, Hideto Ito,* Kenichiro Itami*
Angew. Chem. Int. Ed. 2017, 56, 12224. DOI: 10.1002/anie.201707486
Highlighted in Organometallic Chemistry: Current Trends in Organometallic and Synthetic Chemistry

[Expansion of aromatic ring]

Efficient and rapid access to nanographenes and π-extended fused heteroaromatics is important in materials science. Here we report a Pd-catalyzed efficient one-step annulative πextension (APEX) reaction of PAHs and heteroaromatics, producing various π-extended aromatics. In the presence of a cationic Pd complex, triflic acid, silver pivalate, and diiodobiaryls, diverse unfunctionalized PAHs and heteroaromatics were directly transformed into larger PAHs, nanographenes, and π-extended fused heteroaromatics in a single step. In the reactions affording [5]helicene substructures, simultaneous dehydrogenative ring closures occur at the fjord regions to form unprecedented larger nanographenes. This successive APEX reaction is notable as it stiches five aryl-aryl bonds by C-H functionalization in a single operation. Moreover, the unique molecular structures, crystal-packing structures, photophysical properties, and frontier molecular orbitals of the thus-formed nanographenes were elucidated

See our latest review on APEX reaction:Angew. Chem. Int. Ed. 2017, 56, early view

Comments by authors:

Mr. Wataru Matsuoka (PhD course student, left)

Dr. Hideto Ito (right)
After first publisment of our 1st generation APEX reaction(Nature Commun. 2015), two years have already passed. Two years ago, Wataru had started the reasearch on the development of 2nd generation APEX reaction and did over 2000 experiments but he have obtained not good results day after day. However he never give up and continue to explore many many conditions, reagents and catalysts, and he finally found great reaction as the 2nd APEX reaction. Congratulations, Wataru!!

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