2026-10-14T03:28:03Z https://api.figshare.com/v2/oai

oai:figshare.com:article/34020467 2026-09-29T02:07:00Z category_1 category_4 category_13 category_14 category_873 category_46 category_734 category_61 category_132 category_135 portal_63 item_type_6 month_year_09_2026

Controlling the Reactivity of 1,3-Diacyl-2-gold Carbenes: [3+2] Annulation with External Imines over Wolff Rearrangement Vikas Ashokrao Sadaphal (11089770) Satish Bhausaheb Dawange (25133768) Pei-Qin Liao (1586926) Hsin-Ru Wu (4810521) Rai-Shung Liu (1393513) Biophysics Biochemistry Genetics Molecular Biology Chemical Sciences not elsewhere classified Immunology Biological Sciences not elsewhere classified Developmental Biology Infectious Diseases Computational Biology mechanistic studies suggest density functional theory aminopyrrole derivatives efficiently wolff rearrangement novel competing wolff rearrangement diacyl gold carbene 2a </ b 1a </ b diacyl gold carbenes gold carbenes gold catalysis wolff reaction pyrrole framework nucleophilic addition dicarbonyl unit 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 <b>1a</b> with <b>2a</b> reveal that the [3+2] annulation pathway is energetically more favorable than the competing Wolff rearrangement. 2026-09-28T00:00:00Z Text Journal contribution 10.1021/acs.orglett.6c03682.s001 https://figshare.com/articles/journal_contribution/Controlling_the_Reactivity_of_1_3-Diacyl-2-gold_Carbenes_3_2_Annulation_with_External_Imines_over_Wolff_Rearrangement/34020467 CC BY-NC 4.0