Mechanism of the N-protecting group dependent annulations of 3-aryloxy alkynyl indoles under gold catalysis: a computational study

Organic & Biomolecular Chemistry
Bing ChengYuanzhi Xia

Abstract

The mechanism of the gold-catalyzed annulations of 3-aryloxy alkynyl indoles developed by Tu et al. was studied by DFT calculations. It was found that both indole derivatives of electron-donating and electron-withdrawing protective groups would first undergo the 5-exo-dig cyclization simultaneously upon activation by cationic [PR(3)Au(+)] species. However, divergent reactivity of the resulting spirocyclic intermediate in competitive 1,2-alkenyl migration and nucleophilic water addition reactions towards C3 was predicted. When protected by electron-donating group, the 1,2-alkenyl migration occurs to generate a tricyclic intermediate, from which an aromatic Claisen rearrangement/nucleophilic addition sequence results in the observed 1,2-phenoxy migration. In case of electron-withdrawing group, the 1,2-alkenyl migration would be unfavorable. Instead, the nucleophilic addition of water oxygen to C3 is more facile, and leads to the hemiketal intermediate. The possible roles of water-cluster and OTf anion as proton shuttles in both reactions were also evaluated.

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Citations

Apr 4, 2019·Organic & Biomolecular Chemistry·Jinqiang KuangYuanzhi Xia
Apr 11, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Yongjia LinYuanzhi Xia
Jul 25, 2013·Chemical Communications : Chem Comm·Benito AlcaideM Rosario Torres
Apr 7, 2015·Chemical Reviews·Ruth Dorel, Antonio M Echavarren
Sep 29, 2021·Journal of the American Chemical Society·Grace L TrammelM Kevin Brown

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