Diels-Alder Reactivity of Triisopropylsilyl Ethynyl Substituted Acenes.

We investigated the Diels-Alder reaction of 6,13-bis(triisopropylsilylethynyl)pentacene (1) with small dienophiles such as (bridged) dihydronaphthalenes/cyclohexenes that yielded adducts at the central ring, the other dienophiles predominantly or exclusively attacked the unsubstituted off-center ring. The difference in regioselectivity was investigated by DFT calculations. Apart from dispersion interactions, it is due to the steric demand of the dienophiles, which need to fit in between the silylethynyl substituents to react at the central ring.

Hydroamination of Triisopropylsilyl Acetylene Sulfur Pentafluoride - a Bench-top Route to Pentafluorosulfanylated Enamines.

Synthetic access to a variety of aliphatic and vinylic pentafluorosulfanylated building blocks remains a major challenge in contemporary organofluorine chemistry hampering its investigation in the context of medicinal chemistry, agrochemistry and functional materials. Herein, we report a bench-top protocol to access the virtually unknown class of α-SF -enamines under mild reaction conditions in good to excellent yields (up to 95 %). This reaction combines the protodesilylation of the commercially available precursor TASP with the in situ hydroamination of HC≡C-SF .

Azaarenes: 13 Rings in a Row by Cyclopentannulation.

Cyclopentannulation was explored as a strategy to access large, stable azaarenes. Buchwald-Hartwig coupling of previously reported di- and tetrabrominated cyclopentannulated N,N'-dihydrotetraazapentacenes furnished stable azaarenes with up to 13 six-membered rings in a row and a length of 3.1 nm.

A Stable Hexaazaoctacene Cruciform σ-Dimer.

Buchwald-Hartwig coupling of a triisopropylsilyl (TIPS)-ethynylated dibromo-N,N'-dihydrotetraazapentacene with 1,4-bis(TIPS-ethynyl)-2,3-diaminonaphthalene furnishes a dihydrohexaazaoctacene. Its oxidation with MnO results in a 7,7'-bi(hexaazaoctacenyl). In addition to eight TIPS-ethynyl groups, the bioctacene motif protects the azaoctacene subunits.