Direct Regio- and Stereoselective Mono- and Polyoxyfunctionalization of Estrone Derivatives at C(sp3)-H Bonds | Sciact - CRIS-system of Boreskov Institute of Catalysis

Direct Regio- and Stereoselective Mono- and Polyoxyfunctionalization of Estrone Derivatives at C(sp3)-H Bonds Full article

Journal

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

Output data

Year: 2022, Volume: 415, Pages: 12-18 Pages count : 7 DOI: 10.1016/j.jcat.2022.09.020

Tags

Biomimetic chemistry; C[sbnd]H activation; Late-stage functionalization; Natural products; Steroids

Authors

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

Affiliations

1	Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russia
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

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)

Late-stage catalytic selective oxidative C-H functionalization at B and C rings of estrone 3-acetate, 17α- and 17β-estradiol 3-acetates with H2O2 in the presence of bioinspired nonheme Mn complexes with N4-donor ligands has been developed. Depending on the ligand architecture and absolute chirality, products of α-hydroxylation or ketonization at C6, or α-hydroxylation at C9, or 9,11-desaturation/C12α-hydroxylation can be obtained in synthetically useful yields; the resulting monooxygenated derivatives can be involved in further selective oxidative transformations to yield polyoxygenated metabolites. The aromatic A ring remains intact under the conditions, and ketonization of the hydroxo groups at C17 is effectively prevented by using hexafluoroisopropanol as strong hydrogen bond donor reaction solvent.

Ottenbacher R.V. , Samsonenko D.G. , Nefedov A.A. , Bryliakov K.P.
Direct Regio- and Stereoselective Mono- and Polyoxyfunctionalization of Estrone Derivatives at C(sp3)-H Bonds
Journal of Catalysis. 2022. V.415. P.12-18. DOI: 10.1016/j.jcat.2022.09.020 WOS Scopus РИНЦ ANCAN OpenAlex

Submitted:	Aug 1, 2022
Accepted:	Sep 19, 2022
Published online:	Sep 30, 2022
Published print:	Nov 1, 2022

Web of science:	WOS:000875426600002
Scopus:	2-s2.0-85139301479
Elibrary:	50357026
Chemical Abstracts:	2022:2574602
Chemical Abstracts (print):	182:48302
OpenAlex:	W4298149872

DB	Citing
Scopus	12
Web of science	12
Elibrary	12
OpenAlex	13