Controlling the Reactivity of 1,3-Diacyl-2-gold Carbenes: [3+2] Annulation with External Imines over Wolff Rearrangement.
- 1Department of Chemistry and College of Semiconductor Research Institute, National Tsing Hua University, Hsinchu300, Taiwan, ROC.
Abstract
Novel [3+2] annulations between imines and 1,3-diacyl gold carbenes have been developed to provide 2-acyl-3-aminopyrrole derivatives efficiently. Mechanistic studies suggest that the reaction is initiated by nucleophilic addition of the imine to the 1,3-diacyl gold carbene, generating a gold carbene-imine intermediate that undergoes intramolecular carbocyclization involving the three-carbon 1,3-dicarbonyl unit and the C═N bond to furnish the pyrrole framework. A competitive reaction in this gold catalysis is the Wolff reaction of the 1,3-diacyl gold carbenes when ynone substrates comprise bulky ketones. Density functional theory (DFT) calculations for the reaction of species 1a with 2a reveal that the [3+2] annulation pathway is energetically more favorable than the competing Wolff rearrangement.
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BibTeX
@article{sadaphal2026controlling,
title = {{Controlling the Reactivity of 1,3-Diacyl-2-gold Carbenes: [3+2] Annulation with External Imines over Wolff Rearrangement.}},
author = {Vikas Ashokrao Sadaphal and Satish Bhausaheb Dawange and Pei-Qin Liao and Hsin-Ru Wu and Rai-Shung Liu},
journal = {Organic letters},
year = {2026},
month = oct,
doi = {10.1021/acs.orglett.6c03682},
url = {https://europepmc.org/article/MED/42912229},
note = {CC BY},
}
RIS
TY - JOUR
TI - Controlling the Reactivity of 1,3-Diacyl-2-gold Carbenes: [3+2] Annulation with External Imines over Wolff Rearrangement.
AU - Vikas Ashokrao Sadaphal
AU - Satish Bhausaheb Dawange
AU - Pei-Qin Liao
AU - Hsin-Ru Wu
AU - Rai-Shung Liu
PY - 2026
DA - 2026/10/01
JO - Organic letters
DO - 10.1021/acs.orglett.6c03682
UR - https://europepmc.org/article/MED/42912229
AB - Novel [3+2] annulations between imines and 1,3-diacyl gold carbenes have been developed to provide 2-acyl-3-aminopyrrole derivatives efficiently. Mechanistic studies suggest that the reaction is initiated by nucleophilic addition of the imine to the 1,3-diacyl gold carbene, generating a gold carbene-imine intermediate that undergoes intramolecular carbocyclization involving the three-carbon 1,3-dicarbonyl unit and the C═N bond to furnish the pyrrole framework. A competitive reaction in this gold catalysis is the Wolff reaction of the 1,3-diacyl gold carbenes when ynone substrates comprise bulky ketones. Density functional theory (DFT) calculations for the reaction of species 1a with 2a reveal that the [3+2] annulation pathway is energetically more favorable than the competing Wolff rearrangement.
SN - 1523-7060
SN - 1523-7052
ER -