[2 + 2] cycloreversion of [4.3.2]propella-1,3,11-trienes: An approach to cyclo[n]carbons from propellane-annelated dehydro[n]annulenes

Yoshito Tobe*, Toshihiko Fujii, Hideki Matsumoto, Kunihiro Tsumuraya, Daisuke Noguchi, Nobuko Nakagawa, Motohiro Sonoda, Koichiro Naemura, Yohji Achiba, Tomonari Wakabayashi

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

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Abstract

As a method to generate all-carbon molecules having highly reactive polyyne units from stable precursors, the [2 + 2] cycloreversion of [4.3.2]propella-1,3,11-triene derivatives was developed. To test the efficiency of this method, the reaction was first applied to simple diethynyl- and dibutadiynyl-substituted propellatrienes, which produced upon UV-irradiation linear hexatriyne and decapentayne derivatives, respectively. Next, dehydro[12]-, [16]-, [18]-, [20]-, and [24]annulene derivatives annelated by the [4.3.2]propellatriene units were prepared as precursors to the corresponding cyclo[n]carbons, a monocyclic form of carbon clusters. Laser-desorption mass spectra of the dehydroannulenes exhibited, in the negative mode, peaks due to the corresponding cyclo[n]carbon anions (n = 12, 16, 18, 20, and 24) formed by successive losses of aromatic indane fragments. Solution photolysis of the dehydro[16]annulene and dehydro[18] annulene derivatives formed reactive polyyne intermediates by [2 + 2] cycloreversion which were intercepted by furan to give the corresponding Diels-Alder adducts. The structures and spectroscopic properties of the dehydroannulenes annelated by the [4.3.2]propellatriene units, the precursors to cyclo[n]carbons, and those annelated by the oxanorbornadiene units, the products of the photolysis in furan, are discussed.

Original languageEnglish
Pages (from-to)1762-1775
Number of pages14
JournalJournal of the American Chemical Society
Volume122
Issue number8
DOIs
StatePublished - 1 Mar 2000

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