Mn Aminopyridine Oxidase Mimics: Switching between Biosynthetic-Like and Xenobiotic Regioselectivity in C-H Oxidation of (-)-Ambroxide | Sciact - CRIS-system of Boreskov Institute of Catalysis

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, Russia
2	Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russia
3	Nikolaev Insitute of Inorganic Chemistry, Pr. Lavrentieva 3, Novosibirsk 630090, Russia
4	Vorozhtsov Novosibirsk Institute of Organic Chemistry, Pr. Lavrentieva 9, Novosibirsk 630090, Russia

Funding (1)

Russian Science Foundation

20-13-00032 (АААА-А20-120071590003-2)

The late-stage Csingle bondH 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.

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 ANCAN OpenAlex

Submitted:	May 7, 2021
Accepted:	May 11, 2021
Published online:	May 19, 2021
Published print:	Jul 1, 2021

Web of science:	WOS:000659863400003
Scopus:	2-s2.0-85107021758
Elibrary:	46821946
Chemical Abstracts:	2021:1251915
Chemical Abstracts (print):	177:239519
OpenAlex:	W3162815068

DB	Citing
Scopus	20
Web of science	18
Elibrary	18
OpenAlex	23