Synthesis and structure of N-substituted (1-ferrocenylethyl)amine derivatives

Abstract

N-Acetyl-(1-ferrocenylethyl)amine (8) was synthesized by N-acylation of (1-ferrocenylethyl)amine (7) in 84% yield. Reaction of N-acetyl-[1-(1 -bromoferrocenyl)ethyl]amine (4) (which was prepared by multistep sequence starting from bromoferrocene) with n-BuLi/ ClCOOEt gave 77% of N-acetyl-N-ethoxycarbonyl-(1-ferrocenylethyl)amine (6) instead of the expected ethyl 1 -[1-(acetamido)ethyl]ferrocene-1-carboxylate (5). Both structures were undoubtedly confirmed by (HR)MS spectroscopy and single crystal X-ray structure analysis.

Synthesis and Conformational Analysis of Methyl N‐Alanyl‐1′‐aminoferrocene‐1‐carboxylate

“…The positions of the IR absorption frequencies of the NH and CO groups are indicators of their involvement in hydrogen bonding. Generally, the bands of hydrogen‐bonded NH groups are observed below 3400 cm –1 , whereas bands of the carbonyl groups (ester or amide) below 1730 cm –1 indicate their participation in hydrogen bonds 6e. However, the ester or amide carbonyl groups of 4 – 6 , which are unable to participate in IHBs due to the absence of hydrogen‐bond donor groups on the juxtaposed Cp ring, are excepted from these rules.…”

Friedel–Crafts acylation of ferrocene with alkynoic acids

“…It also plays a very important role in the ferrocene chemistry enabling an easy access to monoacyl-and 1,1 0 -diacylferrocenes, transformable into plethora of other derivatives via classical functional group transformations [3][4][5][6][7][8]. Numerous ferrocene derivatives prepared in this way found applications as ligands in homogenous catalysis, in material science (e.g.…”

Solid‐Phase Synthesis of Transition‐Metal Complexes

“…[17,58,70,72] All metal-functionalised amino acids 29-38 (Scheme 15) are conceptually similar as the transition-metal complex is located in the side-chain of an a-amino acid. Placing the metal-coordinating moiety (Scheme 17, tris(2,2'-bipyridine)-ruthenium complex 42, [73] chlorine-zinc(II) complex 43 [74] ) or the transition-metal fragment itself (Scheme 18, ferrocene derivatives 44 a [75][76][77] and 44 b, [78] bis(2,2':6',2''-terpyridine)ruthenium(II) derivatives 45 a-45 d [79,80] and porphyrin derivatives 46 a-46 d [81] ) between the carboxy and the amino substituent should give transition-metal-containing building blocks with significantly different properties as compared to side-chain modified a-amino acids (Scheme 15).…”

“…[82][83][84] The chiral ferrocene amino acid (Scheme 18; 44 b; Fcca) has only recently been reported and awaits incorporation into peptides. [78] Incorporation of more than one Fca unit with a direct amide link between two ferrocene units has been realised in diferrocenes 50 a-50 d and triferrocene 50 e (Scheme 21). [75,77,85,86] Acid activation with acid fluorides instead of benzotriazole esters proved advantageous in the amide coupling of ferrocenes.…”