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Highly Enantioselective Bioinspired Epoxidation of Electron-Deficient Olefins with H2O2 on Aminopyridine Mn Catalysts Full article

Journal ACS Catalysis
ISSN: 2155-5435
Output data Year: 2014, Volume: 4, Number: 5, Pages: 1599-1606 Pages count : 8 DOI: 10.1021/cs500333c
Tags asymmetric catalysis, enantioselective, epoxidation, hydrogen peroxide, intermediate, manganese, mechanism
Authors Ottenbacher Roman V. 1,2 , Samsonenko Denis G. 1,3 , Talsi Evgenii P. 1,2 , Bryliakov Konstantin P. 1,2
Affiliations
1 Novosibirsk State University, Pirogova 2, Novosibirsk 630090, Russian Federation
2 Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russian Federation
3 Nikolaev Institute of Inorganic Chemistry, Pr. Lavrentieva 3, Novosibirsk 630090, Russian Federation

Funding (3)

1 Russian Foundation for Basic Research 12-03-00782
2 Russian Foundation for Basic Research 14-03-00102
3 The Ministry of Education and Science of the Russian Federation

Abstract: The asymmetric epoxidation of various electron-deficient olefins with H2O2 in the presence of a novel family of chiral bioinspired bipyrrolidine-derived aminopyridine manganese(II) complexes [LMII(OTf)2] is reported. High enantioselectivities (up to 99% ee) and epoxide selectivities (up to 100%), unprecedented for catalysts of this type, have been achieved; the catalysts perform up to 8500 catalytic turnovers. The presence of electron donors in the catalyst structure substantially enhances the enantioselectivity. Isotopic (18O) labeling studies provide evidence of the formation of the oxomanganese(V) active species. Hammett analysis suggests that the enantioselective epoxidation is rate-limited by the transfer of an electron to the MnVO intermediate, to form a short-lived acyclic (carbocationic) intermediate. In effect, the epoxide stereoconfiguration may be affected by the competition between the rotation around the Cα–Cβ single bond and the epoxide ring collapse.
Cite: Ottenbacher R.V. , Samsonenko D.G. , Talsi E.P. , Bryliakov K.P.
Highly Enantioselective Bioinspired Epoxidation of Electron-Deficient Olefins with H2O2 on Aminopyridine Mn Catalysts
ACS Catalysis. 2014. V.4. N5. P.1599-1606. DOI: 10.1021/cs500333c WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
Submitted: Mar 14, 2014
Accepted: Apr 10, 2014
Published online: Apr 22, 2014
Published print: May 2, 2014
Identifiers:
Web of science: WOS:000335491200043
Scopus: 2-s2.0-84899821969
Elibrary: 21876620
Chemical Abstracts: 2014:603411
Chemical Abstracts (print): 160:636322
OpenAlex: W1972555729
Citing:
DB Citing
Web of science 115
Scopus 119
Elibrary 118
OpenAlex 121
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