Synthesis of stableC-linked ferrocenyl amino acids and their use in solution-phase peptide synthesis

Abstract

Incorporation of ferrocenyl group to peptides is an efficient method to alter their hydrophobicity. Ferrocenyl group can also act as an electrochemical probe when incorporated onto functional peptides. Most often, ferrocene is incorporated onto peptides post-synthesis via amide, ester or triazole linkages. Stable amino acids containing ferrocene as a C-linked side chain are potentially useful building units for the synthesis of ferrocene-containing peptides. We report here an efficient route to synthesize ferrocene-containing amino acids that are stable and can be used in peptide synthesis. Coupling of 2-ferrocenyl-1,3-dithiane and iodides derived from aspartic acid or glutamic acid using n-butyllithium leads to the incorporation of a ferrocenyl unit to the δ-position or ε-position of an α-amino acid. The reduction or hydrolysis of the dithiane group yields an alkyl or an oxo derivative. The usability of the synthesized amino acids is demonstrated by incorporating one of the amino acids in both C-terminus and N-terminus of tripeptides in solution phase.

Understanding the Adsorption Energetics of Growth Polymorphs of Ferrocene Derivatives: Microscopic Thermal Desorption Analysis

“…During AFM studies, the relative humidity (≈50%) and temperature (23–26 °C) of the room are maintained by an air conditioner and a dehumidifier. 2-ferrocenyl-1,3-dithiolane (FcS 2 C 3 ) and 2-ferrocenyl-1,3-dithiane (FcS 2 C 4 ) are synthesized according to the literature. , The chemical structures of the molecules are included in the Supporting Information.…”

Controlling Growth to One Dimension in Nanoislands of Ferrocene-Sugar Derivatives

“…Freshly cleaved HOPG was also characterized prior for comparison of the contrast of clean terraces and terrace edges in both phase and topography. Fc-Sug and Fc-Oxo-Sug were synthesized from 2-ferrocenyl-1,3-dithiane 24 , and the details are provided in SI.…”

Diastereoselective Synthesis of (–)-Bestatin, Epibestatin, Phebestin and (3S,4R)-4-Amino-3-hydroxy-5-phenylpentanoic Acid from an Aldehyde Derived from d-Phenylalanine

“…cules, [32][33][34][35][36][37][38][39][40][41] we recently reported the synthesis of D-threosphinganine, L-erythro-sphinganine and (-)-spisulosine from an aldehyde derived from aspartic acid. 42 In the retrosynthetic analysis, it was anticipated that both bestatin and epibestatin could be synthesized from acid 9 using peptide coupling followed by deprotection of the Boc and MOM groups.…”