Enantioselective gold-catalysis is emerging as a powerful tool in organic synthesis for the stereoselective manipulation of unfunctionalized unsaturated hydrocarbons. Despite the exponential growth, the molecular complexity of common chiral gold complexes generally prevents a complete description of the mechanism steps and activation modes being documented. In this study, we present the results of a combined experimental-computational (DFT) investigation of the mechanism of the enantioselective gold-catalyzed allylic alkylation of indoles with alcohols. A stepwise SN2′-process (i.e. antiauroindolination of the olefin, proton-transfer, and subsequent anti-elimination [Au]−OH) is disclosed, leading to a library of tricyclic-fused indole derivatives. The pivotal role played by the gold counterion, in terms of molecular arrangement (i.e. “folding ef fect”) and proton-shuttling in restoring the catalytic species, is finally documented

Mechanistic Insights into Enantioselective Gold-Catalyzed Allylation of Indoles with Alcohols: The Counterion Effect / Bandini, M.; Bottoni, A.; Chiarucci, M.; Cera, G.; Miscione, G. P.. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - 134:51(2012), pp. 20690-20700. [10.1021/ja3086774]

Mechanistic Insights into Enantioselective Gold-Catalyzed Allylation of Indoles with Alcohols: The Counterion Effect

G. Cera;
2012

Abstract

Enantioselective gold-catalysis is emerging as a powerful tool in organic synthesis for the stereoselective manipulation of unfunctionalized unsaturated hydrocarbons. Despite the exponential growth, the molecular complexity of common chiral gold complexes generally prevents a complete description of the mechanism steps and activation modes being documented. In this study, we present the results of a combined experimental-computational (DFT) investigation of the mechanism of the enantioselective gold-catalyzed allylic alkylation of indoles with alcohols. A stepwise SN2′-process (i.e. antiauroindolination of the olefin, proton-transfer, and subsequent anti-elimination [Au]−OH) is disclosed, leading to a library of tricyclic-fused indole derivatives. The pivotal role played by the gold counterion, in terms of molecular arrangement (i.e. “folding ef fect”) and proton-shuttling in restoring the catalytic species, is finally documented
Mechanistic Insights into Enantioselective Gold-Catalyzed Allylation of Indoles with Alcohols: The Counterion Effect / Bandini, M.; Bottoni, A.; Chiarucci, M.; Cera, G.; Miscione, G. P.. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - 134:51(2012), pp. 20690-20700. [10.1021/ja3086774]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11381/2865325
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