Catalytic Nanoassemblies Formed by Short Peptides Promote Highly Enantioselective Transfer Hydrogenation

Abstract

Self-assembly enables formation of incredibly diverse supramolecular structures with practically important functions from simple and inexpensive building blocks. Here, we show how a semirational, bottom-up approach to create emerging properties can be extended to a design of highly enantioselective catalytic nanoassemblies. The designed peptides comprising as few as two amino acid residues spontaneously self-assemble in the presence of metal ions to form supramolecular, vesicle-like nanoassemblies that promote transfer hydrogenation of ketones in an aqueous phase with excellent conversion rates and enantioselectivities (>90% ee).

A Cu(II)–ATP complex efficiently catalyses enantioselective Diels–Alder reactions

“…Over the past four decades, protein-based ArMs have been widely investigated to achieve a variety of valuable enantioselective transformations [1][2][3][4][5][6] . To precisely characterise the active centres and obtain insight into the reaction mechanisms of ArMs, simple scaffolds of peptides and amino acids have been employed to rationally design artificial metallo-peptides [7][8][9][10][11][12][13] and metalloamino acids [14][15][16][17][18][19][20][21] . In recent years, nucleic acids have aroused much interest among chemists for constructing diverse nucleic acid-based ArMs for enantioselective catalysis.…”

Multivalent display of chemical signals on self‐assembled peptide scaffolds

“…Ac-K 4 (ChaKChaE) 2 -NH 2 Lysine residues 3C [153] Ac-K 2 (ChaKChaE) 2 -NH 2 Lysine residues 3C [153] Ac-E 4 (ChaKChaE) 2 -NH 2 Glutamic acid residues 3C [153] Ac-E(CH 2 CHO)EEEAAAVVVK(C 16 )-NH 2 Silver nanoparticles 3C [154] Fmoc-FFECG Silver nanoparticles 3C [155] C 16 -V 3 A 3 K 4 -NH 2 Folate 3D [156] CKKAAVVK-C 12 KLVWLPK-NH2 3D [157] FFERGD 10-hydroxycamptothecin (HCPT)/cisplatin 3D [158] (VPGVG) 80 (VPGSG) 60 EgA1 3D [159] Nap-G D F D F Phosphate/YSV 3D [160] PhAc-FFAG LDD 3D [16] LVFFGFLG RGD/camptothecin 3D [161] Ac-IHIHIQI-NH 2 Histidine residues 3E [162][163][164] Ac-IHIHIYI-NH 2 Histidine residues 3E [163] Im-KLVFFAL-NH 2 Lysine residues/imidazole groups 3E [165] Ac-KLVFFAL-NH 2 Lysine residues 3E [166] Sialic acid 3F [167,168] AQZ/near-infrared quantum dots/Alexa Fluor 633 3F [169] Ac-HLVFFAL-NH 2 Histidine residues/hemin 3E [170] VK2H (HSG(VK) 4 V D PPT(KV) 4 -NH 2 ) Histidine residues 3E [171] Phenylalanine Zn 2+ 3E [172] 1,4,5,8-naphthalenetetracarboxylic acid diimide Proline residues 3E [173] PFE-C 12 Proline residues 3E [174] PEF-C 12 Proline residues 3E [174] PAEPKI-C 16 Proline residues 3E [175] C 10 -FFVK Lysine residues/Fmoc-Tyrosine 3E [176] Ac-LHLHLQL-NH 2 Histidine residues/hemin 3E [177] Ac-LHLHLFL-NH 2 Histidine residues/hemin 3E [177] Ac-LILHLFL-NH 2 Histidine residues/hemin 3E [177] HN-D PL-CONH-C 16 D-proline/leucine residues/IrCp* 3E [178] KKAAVV(K)-C 12 RTL (RTLAFVRFK) 3F [179] SFEEA...…”

“…Korendovych and coworkers have also developed self-assembled peptide materials for the catalysis of oxidation and reduction reactions. [164,178] They screened their series of 15 β-sheet-forming amphipathic heptamer peptides, which were originally screened for Zn 2+ -dependent esterase activity as mentioned previously, for Cu 2 + -dependent oxidative function. [164] Fibrous assemblies of the same Recently, they also developed peptide amphiphiles for transitionmetal-assisted enantioselective reduction of ketones.…”

“…[164] Fibrous assemblies of the same Recently, they also developed peptide amphiphiles for transitionmetal-assisted enantioselective reduction of ketones. [178] Inspired by…”

Exploring the copper binding ability of Mets7 hCtr‐1 protein domain and His7 derivative: An insight in Michael addition catalysis

“…These hybrid systems, applied to the asymmetric Diels‐Alder and Michael addition reactions on α,β‐unsaturated carbonyl compounds, afforded the desired products in moderate‐to‐good enantioselective levels. Recently, starting from ATCUN motif, 30,31 a Cu (II)‐ and Ni (II)‐binding sequence found at the N ‐terminus of many naturally occurring proteins, ultrashort peptides were developed as iridium binding catalytic systems for asymmetric transfer hydrogenation of substituted ketones in water 32,33 . The same scaffolds were successfully employed in the preparation of cobalt‐based hybrid electrocatalysts, for the selective six‐electron reduction of nitrite and hydroxylamine intermediates to ammonium in aqueous buffer 34,35 …”