Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Asymmetric Epoxidation vs syn-Hydroxy-Acyloxylation of Olefins in the Presence of Sterically Demanding Nonheme Manganese Complexes. / Sherstyuk, Varvara A.; Ottenbacher, Roman V.; Talsi, Evgenii P. и др.
в: ACS Catalysis, Том 14, № 1, 05.01.2024, стр. 498-507.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Asymmetric Epoxidation vs syn-Hydroxy-Acyloxylation of Olefins in the Presence of Sterically Demanding Nonheme Manganese Complexes
AU - Sherstyuk, Varvara A.
AU - Ottenbacher, Roman V.
AU - Talsi, Evgenii P.
AU - Bryliakov, Konstantin P.
N1 - The authors thank the Ministry of Science and Higher Education of the Russian Federation for the financial support of this work and acknowledge the access to the facilities of the shared research center “National center of investigation of catalysts”, kindly provided by the Boreskov Institute of Catalysis.
PY - 2024/1/5
Y1 - 2024/1/5
N2 - Herewith, we present another facet of the versatile catalytic reactivity of bulky bis-amino-bis-pyridylmethyl Mn complexes: besides highly enantioselective (up to 99% ee) epoxidation, benzhydryl-substituted Mn catalysts have been found to convert olefinic substrates into the products of syn-addition to the C═C bond, hydroxy-carboxylates, that can prevail under certain conditions. The mechanism of syn-hydroxy-acyloxylation is discussed, with the data obtained providing evidence in favor of the so far lacking direct enantioselective OH and OC(O)R transfer from the high-valent Mn active species to the olefinic C═C group. Such a mechanism is conceptually reminiscent of Rieske dioxygenases that catalyze enantioselective 1,2-dihydroxylation of C═C bonds, simultaneously incorporating two cis-ligands from the reactive metal center into the resulting diol in a syn-selective fashion.
AB - Herewith, we present another facet of the versatile catalytic reactivity of bulky bis-amino-bis-pyridylmethyl Mn complexes: besides highly enantioselective (up to 99% ee) epoxidation, benzhydryl-substituted Mn catalysts have been found to convert olefinic substrates into the products of syn-addition to the C═C bond, hydroxy-carboxylates, that can prevail under certain conditions. The mechanism of syn-hydroxy-acyloxylation is discussed, with the data obtained providing evidence in favor of the so far lacking direct enantioselective OH and OC(O)R transfer from the high-valent Mn active species to the olefinic C═C group. Such a mechanism is conceptually reminiscent of Rieske dioxygenases that catalyze enantioselective 1,2-dihydroxylation of C═C bonds, simultaneously incorporating two cis-ligands from the reactive metal center into the resulting diol in a syn-selective fashion.
KW - asymmetric catalysis
KW - biomimetic chemistry
KW - epoxidation
KW - hydrogen peroxide
KW - manganese
KW - syn-addition
UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85181805299&origin=inward&txGid=d7ee08bd83606a1f84c59f1f2f282b8e
UR - https://www.mendeley.com/catalogue/b72aba5f-6548-3962-bcc1-f17e62b7176d/
U2 - 10.1021/acscatal.3c04832
DO - 10.1021/acscatal.3c04832
M3 - Article
VL - 14
SP - 498
EP - 507
JO - ACS Catalysis
JF - ACS Catalysis
SN - 2155-5435
IS - 1
ER -
ID: 61294334