Straightforward synthesis of 5-bromopenta-2,4-diynenitrile and its reactivity towards terminal alkynes: a direct access to diene and benzofulvene scaffolds

Chemistry : a European Journal
Nicolas KerisitYann Trolez

Abstract

The high-yielding synthesis of 5-bromopenta-2,4-diynenitrile (BrC5 N) was achieved for the first time. Its reactivity with triisopropylsilylacetylene and triisopropylsilylbutadiyne in the presence of copper and palladium as co-catalysts and diisopropylamine was evaluated. It revealed an unprecedented cascade reaction leading to a diene in one case and to a benzofulvene in the other case, with a unique structure. Both of them were characterized by X-ray crystallography, among other techniques. The mechanism of the reaction leading to the diene was investigated experimentally. Theoretical calculations at the DFT level suggest that the mechanism leading to the benzofulvene relies on a hexa-dehydro Diels-Alder (HDDA)-type of mechanism. This work constitutes an example of an unanticipated reactivity leading to an important increase of chemical complexity.

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Citations

Aug 14, 2015·The Journal of Organic Chemistry·Daniel J MarellKeith T Kuwata
Mar 25, 2016·Journal of the American Chemical Society·Junhua ChenThomas R Hoye
Apr 20, 2016·The Journal of Organic Chemistry·Nicolas KerisitYann Trolez
Jun 9, 2016·Journal of the American Chemical Society·Tao WangThomas R Hoye
Jul 12, 2016·The Journal of Physical Chemistry Letters·Baptiste JoallandLudovic Biennier
Dec 30, 2016·The Journal of Organic Chemistry·Bartłomiej PigulskiSławomir Szafert
Jan 21, 2016·Chemistry : a European Journal·Wenbo LiJunliang Zhang
Jul 7, 2017·Organic & Biomolecular Chemistry·Romain LignyYann Trolez
Jan 29, 2016·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Manuel YañezJean-Claude Guillemin
Jul 13, 2018·Organic Letters·Yuanxian Wang, Thomas R Hoye

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