Reactions of HDDA-Derived Benzynes with Perylenes: Rapid Construction of Polycyclic Aromatic Compounds

Abstract

Benzynes produced by the thermal cycloisomerization of tetrayne substrates [i.e., by the hexadehydro-Diels–Alder (HDDA) reaction] react with perylenes to produce novel naphthoperylene derivatives. Cyclic voltammetry and absorption and emission properties of these compounds are described. DFT studies shed additional light on the dearomatization that accompanies the reaction as well as some of the spectroscopic behavior.

Direct observation ofo-benzyne formation in photochemical hexadehydro-Diels–Alder (hν-HDDA) reactions

“…Nevertheless, an additional band can be observed in the longer wavelength regime (460-510 nm), which cannot be attributed to the simple 1 : 1 trapping product, but might belong to a double (2 : 1) adduct structure with extended conjugation. 47 Meanwhile, although values of the factors a and b are determined with some uncertainty, we found that alternations of a (Fig. 5e) or b (Fig.…”

“…An alternative strategy for trapping o-benzyne is its reaction with species containing -C]Cbonds such as in a p-conjugated system reported recently (without time resolution). 12,15,26,47,83 We also made use of this reaction, but again employing femtosecond time-resolved techniques. The trapping product is expected to absorb in the >400 nm wavelength region where the transient absorption of the reactant bis-diynes is sufficiently weak to allow the largely unhindered observation of the trapping products.…”

“…The trapping product is expected to absorb in the >400 nm wavelength region where the transient absorption of the reactant bis-diynes is sufficiently weak to allow the largely unhindered observation of the trapping products. Among the reported options, perylene, with its absorption in the 400-450 nm region, 47 is ideal for our application. In such cases, we have to consider that the intermolecular trapping process occurs as a bimolecular reaction with diffusion-controlled kinetics.…”

Annulative π‐Extension (APEX): Rapid Access to Fused Arenes, Heteroarenes, and Nanographenes

“…In a recent example, bay‐region APEX reactions of perylene derivatives 32 with tetraynes 31 through hexadehydro‐Diels–Alder (HDDA) reactions have been reported by Hoye and co‐workers (Scheme ) . In this reaction, simply heating induces the thermal cycloisomerization of the tetrayne to form alkynylbenzyne 34 , which then undergoes bay‐region APEX reactions to produce naphthoperylene derivatives 33 .…”

The Diels–Alder Reaction for the Synthesis of Polycyclic Aromatic Compounds

“…Carrying out the HDDA reaction in the presence of perylenes led to trapping of the intermediately formed benzynes by the Diels–Alder reaction with perylene core (Scheme ) …”