2026-10-12T10:09:44Z https://api.figshare.com/v2/oai

oai:figshare.com:article/32416151 2026-09-17T15:13:31Z category_1 category_4 category_146 category_8 category_13 category_14 category_21 category_873 category_46 category_734 portal_63 item_type_3 month_year_09_2026

A Bifunctional Aminoxyl–Bipyridine Peptide Catalyst for the Atroposelective Copper-Catalyzed Aerobic Oxidation of Biaryl Diols Halle M. Marvich (19144774) Olivia C. Langner (10710272) Nicolò Tampellini (11232414) Scott J. Miller (1308798) Biophysics Biochemistry Space Science Microbiology Genetics Molecular Biology Biotechnology Chemical Sciences not elsewhere classified Immunology Biological Sciences not elsewhere classified venerable bipyridine ligand secondary kinetic resolution order kinetic profile mechanistic studies reveal ligand class remains historically synthetically challenging created great interest based metal complex modular chiral variants catalyzed aerobic oxidation cu metal center chiral catalysts aerobic oxidations varying levels unison throughout terminal oxidant significant challenge shown promise particularly severe many others er </ copper ­( containing peptide computational experiments commonly employed combined action cocatalysis involves catalytic cycle bipyridyl motif bipyridyl moieties biaryl diols atroposelective copper >, facilitated Chiral aminoxyl catalysts have shown promise for applications in asymmetric oxidations but have been historically synthetically challenging to develop. The paucity of chiral catalysts is particularly severe in aerobic oxidations when cocatalysis involves the combined action of an aminoxyl species and a Cu-based metal complex. In these oxidations, the venerable bipyridine ligand (bpy) is most commonly employed to bind to the Cu metal center. The utility of bpy ligands, in this context and many others, has created great interest in the development of modular chiral variants. However, the design of efficient chiral versions within this ligand class remains a significant challenge. Herein, we report a bifunctional chiral peptide ligand featuring both an aminoxyl and a bipyridyl motif and demonstrate its utility in the copper­(I)-catalyzed aerobic oxidation of biaryl diols to furnish axially chiral aldehydes. This catalyst was found to efficiently catalyze atroposelective oxidations using ambient air as the terminal oxidant. Additionally, catalyst bifunctionality was found to be essential for enantioselectivity in this desymmetrization, affording axially chiral products in up to >99.5:0.5 <i>er</i>, facilitated by combined initial enantiotopic group selection followed by varying levels of secondary kinetic resolution. Central to catalyst design is the synthesis and incorporation of bipyridylalanine into an aminoxyl-containing peptide. Mechanistic studies reveal a first-order kinetic profile on the catalyst, which, in combination with computational experiments, suggest that the aminoxyl and bipyridyl moieties of a single bifunctional peptide function in unison throughout the catalytic cycle. 2026-06-10T00:00:00Z Dataset Dataset 10.1021/jacs.6c04560.s004 https://figshare.com/articles/dataset/A_Bifunctional_Aminoxyl_Bipyridine_Peptide_Catalyst_for_the_Atroposelective_Copper-Catalyzed_Aerobic_Oxidation_of_Biaryl_Diols/32416151 CC BY-NC 4.0