Mn aminopyridine oxidase mimics: Switching between biosynthetic-like and xenobiotic regioselectivity in C–H oxidation of (-)-ambroxide

Mn aminopyridine oxidase mimics: Switching between biosynthetic-like and xenobiotic regioselectivity in C–H oxidation of (-)-ambroxide Full article

Journal

Journal of Catalysis
ISSN: 0021-9517 , E-ISSN: 1090-2694

Output data

Year: 2021, Volume: 399, Pages: 224-229 Pages count : 6 DOI: 10.1016/j.jcat.2021.05.014

Tags

Biomimetic chemistry; C–H activation; Late-stage functionalization; Natural products; Steroids

Authors

Ottenbacher Roman V. ^1,2 , Samsonenko Denis G. ³ , Nefedov Andrey A. ^1,4 , Talsi Evgenii P. ² , Bryliakov Konstantin P. ^1,2

Affiliations

1	Novosibirsk State University, Pirogova 1, Novosibirsk, 630090, Russian Federation
2	Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk, 630090, Russian Federation
3	Nikolaev Insitute of Inorganic Chemistry, Pr. Lavrentieva 3, Novosibirsk, 630090, Russian Federation
4	Vorozhtsov Novosibirsk Institute of Organic Chemistry, Pr. Lavrentieva 9, Novosibirsk, 630090, Russian Federation

The late-stage C–H oxofunctionalization of (-)-ambroxide with H2O2 in the presence of bioinspired honheme Mn complexes is reported. Adjusting the ligand architecture and absolute chirality, as well as tuning the reaction solvent, allows switching the catalysts’ selectivity between biosynthetic-like and bioorthogonal modes, thus directing the reaction towards either (+)-sclareolide or 2α-hydroxyambroxide, respectively. This opens the ways to 2,12-dihydroxyambroxide, 2α-hydroxysclareolide, ambroxide-2-one, ambroxide-2,12-dione, and several other, including previously unavailable, oxidized metabolites of (-)-ambroxide in synthetically meaningful yields, using the same catalyst systems. © 2021 Elsevier Inc.

Ottenbacher R.V. , Samsonenko D.G. , Nefedov A.A. , Talsi E.P. , Bryliakov K.P.
Mn aminopyridine oxidase mimics: Switching between biosynthetic-like and xenobiotic regioselectivity in C–H oxidation of (-)-ambroxide
Journal of Catalysis. 2021. V.399. P.224-229. DOI: 10.1016/j.jcat.2021.05.014 WOS Scopus РИНЦ

Published print:

Jul 1, 2021

Web of science	WOS:000659863400003
Scopus	2-s2.0-85107021758
Elibrary	46821946
OpenAlex	W3162815068