Construction of 5H‐Dibenzo[c,e]azepine Framework from Dibenzothiophene Dioxides andN‐Benzylimines through S_NAr Reactions

Abstract

Dedicated to Dr. E. Peter Kündig on the occasion of his 75th birthdayTreatment of a mixture of dibenzothiophene dioxides and benzaldehyde N-benzylimines with potassium hexamethyldisilazide induces sequential intermolecular and intramolecular S N Ar reactions to eventually form the corresponding 5H-dibenzo[c,e]azepines without any formation of the conceivable five-membered fluorene derivatives.

Masters of Mediation: MN(SiMe3)2 in Functionalization of C(sp3)−H Latent Nucleophiles

“…With the pioneering work of Yorimitsu in “aromatic metamorphosis” [93] they continued the synthesis of dibenzoazepine 81 by reacting dibenzothiophene dioxides with N ‐benzylimines from aldehydes that serves as dual nucleophiles (Scheme 37). [94] The reaction is induced by KN(SiMe 3 ) 2 and follows a sequential intermolecular and intramolecular S N Ar reactions. Notably, the reaction did not produce the seemingly favourable five‐membered fluorene derivatives.…”

Synthesis of Dithia[5]helicenes and Enantioselective Synthesis of Helically Chiral Thia[6]helicenes via Rh-Catalyzed Intramolecular [2 + 2 + 2] Cycloaddition of Triynes

“…On the other hand, sulfur-containing polycyclic aromatic compounds, as represented by benzothiophene, act as functional molecules, such as organic field-effect transistors (OFETs) and organic light-emitting diodes (OLEDs) . Furthermore, Yorimitsu and co-workers developed a new strategy in the synthetic transformation of a dibenzothiophene skeleton to another dibenzoheterole, which was called “aromatic metamorphosis” . For example, consecutive intermolecular/intramolecular S N Ar reactions of benzothiophene dioxides with anilines gave carbazoles .…”