Manganese Catalyzed Direct Regio- and Stereoselective Hydroxylation of 5α- and 5β-Androstane Derivatives | Sciact - CRIS-system of Boreskov Institute of Catalysis

Manganese Catalyzed Direct Regio- and Stereoselective Hydroxylation of 5α- and 5β-Androstane Derivatives Full article

Journal

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

Output data

Year: 2023, Volume: 425, Pages: 32-39 Pages count : 8 DOI: 10.1016/j.jcat.2023.06.003

Tags

biomimetic chemistryC-H activationhydroxylationlate-stage functionalizationnatural productssteroids

Authors

Ottenbacher Roman V. ¹ , Samsonenko Denis G. ^2,4 , Bryliakova Anna A. ^1,4 , Nefedov Andrey A. ^3,4 , Bryliakov Konstantin P. ⁵

Affiliations

1	Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russian Federation
2	Nikolaev Insitute of Inorganic Chemistry, Lavrentieva 3, Novosibirsk 630090, Russia
3	Vorozhtsov Novosibirsk Institute of Organic Chemistry, Pr. Lavrentieva 9, Novosibirsk 630090, Russia
4	Novosibirsk State University, Pirogova 1, Novosibirsk 630090, Russia
5	Zelinsky Institute of Organic Chemistry RAS, Leninsky Pr. 47, Moscow 119991, Russia

Funding (3)

1	Russian Science Foundation	22-73-00080
2	Ministry of Science and Higher Education of the Russian Federation	FWUZ-2021-0001 (121031700321-3)
3	Ministry of Science and Higher Education of the Russian Federation	0238-2021-0005 (АААА-А21-121011490018-2)

Herewith we report late-stage catalytic selective oxidative functionalization of several steroids with a common gonane core, namely androstane derivatives 5α-androsterone-3-acetate, 5β-androstan-17β-ol-3-one (etiocholan-17β-ol-3-one), 17β-acetoxy-5β-androstan-3-one, and 5β-pregnane-3,20-dione, at C–H groups in the presence of chiral bis-amino-bis-pyridylmethyl and structurally related Mn complexes, using H2O2 as terminal oxidant. Depending on the steric demand and absolute chirality of the catalyst, mono-hydroxylation at A, B, or C rings is achieved in up to 58 % isolated yield. Strongly hydrogen-bond donating solvent hexafluoroisopropanol (HFIP) effectively protects the C17–OH group in etiocholan-17β-ol-3-one from ketonization, thus providing an opportunity to obtain 6,17- and 12,17-dihydroxy androstane derivatives without using protecting groups.

Ottenbacher R.V. , Samsonenko D.G. , Bryliakova A.A. , Nefedov A.A. , Bryliakov K.P.
Manganese Catalyzed Direct Regio- and Stereoselective Hydroxylation of 5α- and 5β-Androstane Derivatives
Journal of Catalysis. 2023. V.425. P.32-39. DOI: 10.1016/j.jcat.2023.06.003 WOS Scopus РИНЦ AN OpenAlex

Submitted:	Apr 27, 2023
Accepted:	Jun 2, 2023
Published online:	Jun 3, 2023
Published print:	Sep 1, 2023

Web of science:	WOS:001019647000001
Scopus:	2-s2.0-85161551900
Elibrary:	54088988
Chemical Abstracts:	2023:1215874
OpenAlex:	W4379209792

DB	Citing
Scopus	7
Elibrary	5
OpenAlex	7
Web of science	7