Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Manganese catalyzed direct regio- and stereoselective hydroxylation of 5α- and 5β-androstane derivatives. / Ottenbacher, Roman V.; Samsonenko, Denis G.; Bryliakova, Anna A. и др.
в: Journal of Catalysis, Том 425, 09.2023, стр. 32-39.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Manganese catalyzed direct regio- and stereoselective hydroxylation of 5α- and 5β-androstane derivatives
AU - Ottenbacher, Roman V.
AU - Samsonenko, Denis G.
AU - Bryliakova, Anna A.
AU - Nefedov, Andrey A.
AU - Bryliakov, Konstantin P.
N1 - This work was supported by the Russian Science Foundation (#22-73-00080). RVO gratefully acknowledges 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 the Nikolaev Institute of Inorganic Chemistry SB RAS, 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). AAB thanks the access to the supercomputer facilities of the Computing Centre of Novosibirsk State University. Публикация для корректировки.
PY - 2023/9
Y1 - 2023/9
N2 - 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.
AB - 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.
KW - Biomimetic chemistry
KW - C–H activation
KW - Hydroxylation
KW - Late-stage functionalization
KW - Natural products
KW - Steroids
UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85161551900&origin=inward&txGid=a93d87e28b338bcdfd8d35fb44a22826
UR - https://www.mendeley.com/catalogue/84da0364-aa18-322b-962f-f7782a2556b7/
U2 - 10.1016/j.jcat.2023.06.003
DO - 10.1016/j.jcat.2023.06.003
M3 - Article
VL - 425
SP - 32
EP - 39
JO - Journal of Catalysis
JF - Journal of Catalysis
SN - 0021-9517
ER -
ID: 59264846