The aromatic ene reaction

Nature Chemistry
Dawen Niu, Thomas R Hoye

Abstract

The ene reaction is a pericyclic process in which an alkene with an allylic hydrogen atom (the ene donor) reacts with a second unsaturated species (the enophile) to form a new product with a transposed π-bond. The aromatic ene reaction, in which the alkene component is embedded in an aromatic ring, has only been reported in a few (four) instances and has proceeded in low yield (≤6%). Here, we show efficient aromatic ene reactions in which a thermally generated aryne intermediate engages a pendant m-alkylarene substituent to produce a dearomatized isotoluene, itself another versatile but rare reactive intermediate. Our experiments were guided by computational studies that revealed structural features conducive to the aromatic ene process. We proceeded to identify a cascade comprising three reactions: (1) hexadehydro-Diels-Alder (for aryne generation), (2) intramolecular aromatic ene and (3) bimolecular Alder ene. The power of this cascade is evident from the structural complexity of the final products, the considerable scope, and the overall efficiency of these multistage, reagent- and by-product-free, single-pot transformations.

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Citations

Mar 25, 2016·Journal of the American Chemical Society·Junhua ChenThomas R Hoye
Jul 24, 2015·Nature Chemistry·Niko PavličekLeo Gross
Apr 19, 2016·Nature·Teng WangThomas R Hoye
Aug 4, 2016·Organic Letters·Sung-Eun Suh, David M Chenoweth
Aug 17, 2016·Journal of the American Chemical Society·Yuanyuan LiYang Li
Oct 29, 2015·Organic Letters·Ramesh Chingle, William D Lubell
May 27, 2017·Journal of the American Chemical Society·Feng XuThomas R Hoye
Apr 22, 2017·Chemistry : a European Journal·Venkata R SabbasaniDaesung Lee
Feb 22, 2017·Chemical Society Reviews·Jiarong ShiYang Li
Sep 18, 2014·Chemical Communications : Chem Comm·Adam E GoetzNeil K Garg
Oct 19, 2016·Chemical Society Reviews·José-Antonio García-López, Michael F Greaney
Jul 6, 2014·Angewandte Chemie·Da ZhaoZuowei Xie
Apr 28, 2017·Angewandte Chemie·F Matthias Bickelhaupt, Kendall N Houk
May 7, 2014·Angewandte Chemie·Catherine Holden, Michael F Greaney
Oct 2, 2020·Nature·Masao OhashiYi Tang
Jan 8, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Marziyeh E KenariDaniel W Armstrong
Jan 16, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Fabricio R BisognoGonzalo de Gonzalo
Feb 19, 2021·Chemical Reviews·Jiarong ShiYang Li
Mar 30, 2021·European Journal of Organic Chemistry·Sahil AroraThomas R Hoye
Aug 26, 2014·Organic Letters·Brian P WoodsThomas R Hoye
Jun 12, 2019·Journal of the American Chemical Society·Xiao Xiao, Thomas R Hoye
Dec 31, 2016·Journal of the American Chemical Society·Jiarong ShiYang Li
Dec 3, 2014·Journal of the American Chemical Society·Yoshihide MizukoshiMasanobu Uchiyama
Dec 23, 2014·Journal of the American Chemical Society·E Ben HayDennis P Curran
Jan 24, 2019·The Journal of Organic Chemistry·Maggie ChenK N Houk
Mar 4, 2014·Journal of the American Chemical Society·Nam-Kyu LeeYuanzhi Xia
Oct 5, 2018·Journal of the American Chemical Society·Dachuan QiuYang Li

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