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Updated: Jun 14, 2025

Preparation of N-2-alkoxyvinylsulfonamides from N-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines
Published on: January 3, 2018
A Strongly Ambiphilic Ferrocene-Based Cyclic (Alkyl)(amino)carbene - Specific Decomposition to an Enamine by a
Julia Volk1,2, Myron Heinz3, Robin Guthardt1
1Institute of Chemistry, University of Kassel, Heinrich-Plett-Straße 40, 34132, Kassel, Germany.
Abstract:
The recently described crystalline cyclic (alkyl)(amino)carbene with a 1,1'-ferrocenylene (fc) backbone fc(CPh2-C-NMes) (A, Mes=mesityl) is highly reactive due to its particularly pronounced ambiphilicity and is thermally not stable in solution due to an intramolecular insertion of the divalent carbon atom into a methyl C-H bond of the Mes substituent. The closely related congener fc(CPh2-C-N-p-C6H4-tBu) (1) cannot undergo such an insertion reaction. Nevertheless, 1 is too short-lived for isolation due to a rapid 1,2-shift of a phenyl group, furnishing the isomeric cyclic enamine fc[C(Ph)=C(Ph)-N-p-C6H4-tBu] (1') in a specific decomposition process unprecedented for CAACs. Trapping of 1 was possible with carbon monoxide, elemental selenium and with [CuBr(SMe2)], respectively affording the aminoketene 1=C=O, the selenoamide 1=Se and the homoleptic CuI complex [Cu(1)2][CuBr2]. 1 is an even stronger ambiphile than A according to NMR spectroscopic data. Similar to A, 1 does not react with H2, because the experimentally observed intramolecular process is kinetically more favourable according to DFT results.
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