Journal
ORGANIC & BIOMOLECULAR CHEMISTRY
Volume 10, Issue 22, Pages 4417-4423Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2ob25316j
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Funding
- National Natural Science Foundation of China [21002073]
- Wenzhou Science & Technology Bureau [Y20100003]
- Wenzhou University
- Xinmiao Talent Program of Zhejiang Province [2010R424044]
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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 [PR3Au+] 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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