Serendipitous Rediscovery of the Facile Cyclization of Z , Z ‐3,5‐Octadiene‐1,7‐diyne Derivatives to Afford Stable, Substituted Naphthocyclobutadienes

Autor: Jérôme Marrot, Tanguy Jousselin-Oba, Michael M. Haley, Lev N. Zakharov, Joshua E. Barker, Conerd K. Frederickson, Michel Frigoli, Takuya Kodama, Min K. Song, Richard P. Johnson
Přispěvatelé: University of Oregon [Eugene], University of New Hampshire (UNH), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Rok vydání: 2019
Předmět:
Zdroj: ChemPlusChem
ChemPlusChem, Wiley, 2019, Novel Aromatics, 84 (6), pp.665-672. ⟨10.1002/cplu.201800605⟩
ISSN: 2192-6506
Popis: International audience; The serendipitous isolation of very small amounts of two naphthocyclobutadiene (NCB) derivatives has led to the computational re-examination of the electrocyclization of Z,Z-3,5-octadiene-1,7-diyne as well as the experimental and computational study of diethynylindeno[2,1-a]fluorene derivatives that contain the 3,5-octadiene-1,7-diyne motif as part of a larger π-framework. In both cases the calculated potential energy surface strongly implicates two successive electrocyclic reactions to afford the antiaromatic products. With the octadienediyne fragment locked in the reactive conformation, the postulated diethynylindeno[2,1-a]fluorene intermediates afford the NCBs in modest to good yields. X-ray crystallography of four NCBs as well as NICS-XY scan calculations show that the paratropic motif is located primarily in the benzocyclobutadiene fragment within the larger π-scaffold.
Databáze: OpenAIRE
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