Solid‐Phase Synthesis of Chiral Modular Ferrocene‐Based Peptides

Abstract

Ferrocene-containing tripeptides with one to two ferrocene building blocks were prepared by solid-phase peptide synthesis (SPPS) using Fmoc-protected 1Ј-aminoferrocene-1-carboxylic acid (Fca). The conformations of the tripeptides were analysed by spectroscopic and theoretical methods. The im-

Solid‐Phase Synthesis of Transition‐Metal Complexes

“…Such well-defined hetero-oligomers could find useful applications as receptors, sensors, sensitisers, molecular wires, devices and switches, see for example, references [79,85,89,[94][95][96].…”

“…[88] Two ferrocene units have been linked together on solid support (TentaGel resin with an acid-labile Wang linker [6] ) by using Fmoc-protected a-amino acids and Fmoc-Fca-H (49 a) giving the tripeptide Ac-Fca-Fca-Ala-OH (Scheme 23, 53). [89] In a fully analogous fashion the tripeptides with one internal Fca unit Ac-Ala-Fca-Gly-OH (54 a), Ac-Ala-FcaAla-OH (54 b) and Ac-Gly-Fca-Phe-OH (54 c) were prepared by using Fmoc protecting groups on TentaGel-Wang resin. [89,90] The bis(2,2':6',2''-terpyridine)ruthenium(II) amino acid 45 a (Scheme 18) has been coupled to ferrocene units in solution by using HOBt activation of the acid and deprotonation of the unreactive amine with the Schwesinger phosphazene base P 1 tBu (P 1 tBu = tert-butylimino-tris(dimethylamino)phosphorane) giving ferrocene-and ruthenium(II)-containing amides 55 a-55 c (Scheme 24).…”

“…[89] In a fully analogous fashion the tripeptides with one internal Fca unit Ac-Ala-Fca-Gly-OH (54 a), Ac-Ala-FcaAla-OH (54 b) and Ac-Gly-Fca-Phe-OH (54 c) were prepared by using Fmoc protecting groups on TentaGel-Wang resin. [89,90] The bis(2,2':6',2''-terpyridine)ruthenium(II) amino acid 45 a (Scheme 18) has been coupled to ferrocene units in solution by using HOBt activation of the acid and deprotonation of the unreactive amine with the Schwesinger phosphazene base P 1 tBu (P 1 tBu = tert-butylimino-tris(dimethylamino)phosphorane) giving ferrocene-and ruthenium(II)-containing amides 55 a-55 c (Scheme 24). [79] Cyclic voltammetry indicates that the two ferrocene units in 55 c are electronically uncoupled.…”

C2‐Symmetric Ferrocene–Bis(ureido)peptides: Synthesis, Conformation and Solid‐State Structure

“…This combination of methods has been previously successfully applied for analysing bioconjugates of ferrocene derivatives. [19,23,[25][26][27]31,33,36,38] The hydrogen-acceptor site of hydrogen bonds is easily seen by IR spectroscopy. The IR data of 3 indicate hydrogen bonds to the ester carbonyl CO ester , whereas in 4 hydrogen bonds to the amide carbonyl CO amide are observed ( Table 1).…”

Solid‐Phase Synthesis of Peptide Libraries Combining α‐Amino Acids with Inorganic and Organic Chromophores

“…[29,30,31] For example, 1) a series of trisheteroleptic ruthenium(II) complexes has been recently prepared by solid-phase methods by Meggers for potential application as acetylcholinesterase inhibitors, [32] 2) peptide-tethered platinum(II) complexes for use as cytostatic drugs have been prepared by automated parallel solid-phase synthesis by van Boom and Reedijk, [33] 3) a library of iridiumA C H T U N G T R E N N U N G (III) acetylacetonato complexes has been synthesised by Li as red-phosphorescent emitters in organic light-emitting diodes (OLEDs) [34] and 4) ferrocene-incorporating peptides have been constructed by SPPS techniques by MetzlerNolte and Heinze. [35,36] In this work we extend the SPPS approach to incorporate the artificial metallo amino acid 1 d into multichromophore systems with suitably substituted organic dyes (coumarins, naphthalene, anthracene, fluorene). The aim is to develop a fast, simple and reliable high-throughput technique for synthesising and screening of potential light-harvesting arrays.…”