Synthesis of ferrocene amides and esters from aminoferrocene and 2-substituted ferrocenecarboxylic acid and properties thereof

Abstract

International audienceDifferent ferrocenecarboxamides were synthesized from aminoferrocene and various acid coupling partners such as N-alpha-Boc-L-tryptophan and N-protected sugar amino acids ( N-Boc-3-amino-3-deoxy-1,2-O-isopropylidene-alpha-D-ribofuranoic acid, N-Boc-3-amino-3-deoxy-1,2-O-isopropylidene-alpha-D-xylofuranoic acid and their corresponding homo- and hetero-dimers). Similarly, reactions between 2-aminoethyl ferrocenecarboxylate and N-protected sugar amino acids afforded compounds with a carboxamide functional group remotely positioned from the ferrocene core. The X-ray diffraction structure of one of them showed the presence of an intermolecular hydrogen bond between the amide functional groups. Carbonylamino ( or carbonyloxy) and oxycarbonyl 1,2-disubstituted ferrocenes were prepared either as racemic mixtures or in enantiomerically pure ( S-P) form. Their electrochemical evaluation revealed distinctive features. Interestingly, the enantiomerically pure ferrocene diester showed a large potential shift (+45 mV) in the presence of L-glutamic acid. Finally, some of the synthesized ferrocenes were evaluated for their antibacterial, antifungal and antiproliferative ( MCF-7) activities

2-Aminophenones, a common precursor to N-aryl isatins and acridines endowed with bioactivities

“…1 41 Microanalyses were performed on a Flash 1112 Thermo Fisher elemental analyzer. Iodoferrocene, 42 2-iodobenzothiophene, 43 2iodobenzofuran 43 and 2-iodofuran 44 were prepared as described previously.…”

Haloferrocenes: Syntheses and Selected Reactions

“…This has been realized by Nassar, Erb, Radha Krishna et al, who transformed 2iodoferrocenecarboxylic acid (110), in racemic (rac-110) as well as in enantiopure form [(S p )-110] into the ester 111, from which the Boc-protected ferrocenyl-1,2-dicarboxylate 112 was obtained in the presence of 0.8 equivalents of copper (I) oxide in 54% yield in racemic as well as in enantiopure form (Scheme 36). 72 More recently, Csámpai et al reported a related reaction in which a sulfur atom was attached to the ferrocene moiety via an intramolecular reaction. In the intramolecular substitution, thioamides such as 113 were converted into ferrocenothiazines like 114 in up to 93% yield in the presence of copper(I) iodide and N,N′-dimethylethylenediamide (DMEDA) (10 mol% each) (Scheme 37).…”

On the N‐Arylation of Acetamide Using 2‐, 3‐ and 1’‐Substituted Iodoferrocenes**

“…Indeed, whereas iodoferrocene can react with amides by recourse to copperbased systems, [16] the involvement of 2-substituted derivatives in such couplings is far less obvious due to competitive deiodination. [16c] While continuing our work dedicated to the synthesis of ferrocene amides, [17] we recently reported the successful N-arylation using iodoferrocene of a large range of carboxamides. [18] In the continuation of our efforts to develop synthetic methods in the ferrocene series and to understand their specific behavior, [17,19] we were eager to study the effect of an additional substituent at the 2-, 3-or 1'-position of iodoferrocene on the amide N-arylation.…”

“…[16c] While continuing our work dedicated to the synthesis of ferrocene amides, [17] we recently reported the successful N-arylation using iodoferrocene of a large range of carboxamides. [18] In the continuation of our efforts to develop synthetic methods in the ferrocene series and to understand their specific behavior, [17,19] we were eager to study the effect of an additional substituent at the 2-, 3-or 1'-position of iodoferrocene on the amide N-arylation. To this goal, 35 substituted iodoferrocenes were engaged in the copper-mediated N-arylation reaction, leading to 28 original N-ferrocenyl acetamides, isolated in moderate to good yields which were tentatively linked to the structural and electronic features of the iodo partners.…”

“…Crystal data for 6f. C13H13FeNO2, M = 271.09, T = 150(2) K, monoclinic, P 21/c, a = 7.1408(12), b = 16.661(3), c = 9.5968(17) Å, β = 102.302(6) °, V = 1115.5(3) Å 3 , Z = 4, d = 1.614 g cm-3 , μ = 1.338 mm-1 . A final refinement on F 2 with 2568 unique intensities and 157 parameters converged at ωR(F 2 ) = 0.0670 (R(F) = 0.0292) for 2199 observed reflections with I > 2σ(I).…”