Direct regio- and stereoselective mono- and polyoxyfunctionalization of estrone derivatives at C(sp3)-H bonds

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Direct regio- and stereoselective mono- and polyoxyfunctionalization of estrone derivatives at C(sp³)-H bonds. / Ottenbacher, Roman V.; Samsonenko, Denis G.; Nefedov, Andrey A. и др.

в: Journal of Catalysis, Том 415, 11.2022, стр. 12-18.

Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование

BibTeX

@article{443d098777644b119daed0201bf28589,

title = "Direct regio- and stereoselective mono- and polyoxyfunctionalization of estrone derivatives at C(sp3)-H bonds",

abstract = "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.",

keywords = "Biomimetic chemistry, C[sbnd]H activation, Late-stage functionalization, Natural products, Steroids",

author = "Ottenbacher, {Roman V.} and Samsonenko, {Denis G.} and Nefedov, {Andrey A.} and Bryliakov, {Konstantin P.}",

note = "Funding Information: This work was supported by the Russian Science Foundation (#22-73-00080). RVO and KPB gratefully acknowledge the access to the facilities of the shared research center “National center of investigation of catalysts”, kindly provided by Boreskov Institute of Catalysis. DGS acknowledges budget funding by the Ministry of Science and Higher Education of the Russian Federation for Nikolaev Institute of Inorganic Chemistry, project 121031700321-3 (X-ray measurements). AAN is grateful to the Ministry of Science and Higher Education of the Russian Federation, project 1021051503141-0-1.4.1 for Vorozhtsov Novosibirsk Institute of Organic Chemistry (HR-MS measurements). Publisher Copyright: {\textcopyright} 2022 Elsevier Inc.",

year = "2022",

month = nov,

doi = "10.1016/j.jcat.2022.09.020",

language = "English",

volume = "415",

pages = "12--18",

journal = "Journal of Catalysis",

issn = "0021-9517",

publisher = "Academic Press Inc.",

}

RIS

TY - JOUR

T1 - Direct regio- and stereoselective mono- and polyoxyfunctionalization of estrone derivatives at C(sp3)-H bonds

AU - Ottenbacher, Roman V.

AU - Samsonenko, Denis G.

AU - Nefedov, Andrey A.

AU - Bryliakov, Konstantin P.

N1 - Funding Information: This work was supported by the Russian Science Foundation (#22-73-00080). RVO and KPB gratefully acknowledge the access to the facilities of the shared research center “National center of investigation of catalysts”, kindly provided by Boreskov Institute of Catalysis. DGS acknowledges budget funding by the Ministry of Science and Higher Education of the Russian Federation for Nikolaev Institute of Inorganic Chemistry, project 121031700321-3 (X-ray measurements). AAN is grateful to the Ministry of Science and Higher Education of the Russian Federation, project 1021051503141-0-1.4.1 for Vorozhtsov Novosibirsk Institute of Organic Chemistry (HR-MS measurements). Publisher Copyright: © 2022 Elsevier Inc.

PY - 2022/11

Y1 - 2022/11

N2 - 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.

AB - 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.

KW - Biomimetic chemistry

KW - C[sbnd]H activation

KW - Late-stage functionalization

KW - Natural products

KW - Steroids

UR - http://www.scopus.com/inward/record.url?scp=85139301479&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/0cf30df5-a3c0-3fb7-9229-c0c77b8adf94/

U2 - 10.1016/j.jcat.2022.09.020

DO - 10.1016/j.jcat.2022.09.020

M3 - Article

AN - SCOPUS:85139301479

VL - 415

SP - 12

EP - 18

JO - Journal of Catalysis

JF - Journal of Catalysis

SN - 0021-9517

ER -

ID: 38158260