Amino acid-based tweezers: The role of turn-like conformation in the binding of copper(II)

“Backdoor Induction” of Chirality: Asymmetric Hydrogenation with Rhodium(I) Complexes of Triphenylphosphane-Substituted β-Turn Mimetics

“…We have reported that templates based on amino acids bridged with a rigid cis-enediyne moiety have predefined turnlike conformation while maintaining enough flexibility to adjust upon addition of metal ions. 7 Moreover, the close resemblance with one class of β-turn geometry was found when applying geometric analysis on C α surrogates in our templates (Chart 1b).…”

Enediyne-Comprising Amino Aldehydes in the Passerini Reaction

“…Motivated by their biological importance, many cyclic and acyclic enediyne derivatives were prepared and their biological activities evaluated. − Apart from their role in biologically relevant processes, enediynes are versatile building blocks for the construction of complex aromatic systems through thermal or photochemical activation. − Furthermore, rigid, stable, and spatially well-directed enediyne motif can be exploited as an inducer of turn-like conformation. In our previous studies, we showed that enediyne-based small molecule tweezers are efficient Cu­(II) atom binders . Comparison of the stability of studied complexes with those reported for histidine-rich peptide fragments with high affinity for copper­(II) revealed that enediyne tweezers effectively mimic properties of copper­(II) binding peptides.…”

“…In our previous studies, we showed that enediyne-based small molecule tweezers are efficient Cu(II) atom binders. 12 Comparison of the stability of studied complexes with those reported for histidine-rich peptide fragments with high affinity for copper(II) revealed that enediyne tweezers effectively mimic properties of copper(II) binding peptides. It is noteworthy that in many proteins, the proline residue is found in the vicinity of Cu(II) binding site, mostly preceding histidine residue.…”

1,2-Dihaloalkenes in Metal-Catalyzed Reactions

“…82 (Z)-1,2-Dichloroethene [(Z)-8a] was used to prepare nitrogen donor enediyne chelates and tweezers based on amino acids 171b (entry 2). 70,83 In their fundamental study of enediyne isomers, Bowling and Mc-Mahon used a Negishi coupling between (E/Z)-1,2-dibromoethene 8b (ratio E/Z 2:1) and (trimethylsilyl)acetylene to produce enediyne 171c (entry 3); 84 the same E/Z ratio was observed in the final product. (E)-2,3-Dihalobutenedioic derivatives (E)-1b were used by a number of research groups to prepare highly electrophilic unsaturated esters, nitriles, and aldehydes 171d (entry 4); 85 these are mainly valued for their photochromic properties.…”