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Enantioselective Epoxidations of Olefins with Various Oxidants on Bioinspired Mn Complexes: Evidence for Different Mechanisms and Chiral Additive Amplification Full article

Journal ACS Catalysis
ISSN: 2155-5435
Output data Year: 2016, Volume: 6, Number: 2, Pages: 979-988 Pages count : 9 DOI: 10.1021/acscatal.5b02299
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 (2)

1 Federal Agency for Scientific Organizations V.44.2.4.
2 Russian Foundation for Basic Research 14-03-00102

Abstract: It has been demonstrated that chiral manganese aminopyridine complexes [LMnII(OTf)2] are able to epoxidize olefins with excellent enantioselectivities (up to 99% ee, several examples) with various terminal oxidants (H2O2, alkyl hydroperoxides, peroxyacids, and iodosylarenes). The mechanisms of enantioselective olefin epoxidations on aminopyridine manganese(II) complexes [LMnII(OTf)2] with different oxidants are considered. The analysis of reaction products and epoxidation enantioselelctivity, Hammett correlations, and isotopic (18O) labeling studies bear evidence in favor of the formation of different oxidizing species in the presence of different terminal oxidants. The addition of cocatalytic additives (carboxylic acid or H2O) dramatically changes the catalytic behavior of catalyst systems Mn complex/hydrogen peroxide and Mn complex/alkyl hydroperoxide; in the presence of additives, the catalyst systems with H2O2 and alkyl hydroperoxides demonstrate very similar behaviors. Remarkably, in the presence of chiral additive Boc-protected (l)-proline, achiral Mn aminopyridine complexes catalyze the epoxidation of chalcone in an enantioselective fashion (with up to 60% ee), representing a rare example of chiral environment amplification.
Cite: Ottenbacher R.V. , Samsonenko D.G. , Talsi E.P. , Bryliakov K.P.
Enantioselective Epoxidations of Olefins with Various Oxidants on Bioinspired Mn Complexes: Evidence for Different Mechanisms and Chiral Additive Amplification
ACS Catalysis. 2016. V.6. N2. P.979-988. DOI: 10.1021/acscatal.5b02299 WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
Submitted: Oct 14, 2015
Accepted: Dec 24, 2015
Published online: Jan 12, 2016
Published print: Feb 5, 2016
Identifiers:
Web of science: WOS:000369774900059
Scopus: 2-s2.0-84957537042
Elibrary: 26861051
Chemical Abstracts: 2015:2104411
Chemical Abstracts (print): 164:187629
OpenAlex: W2236588896
Citing:
DB Citing
Web of science 60
Scopus 62
Elibrary 64
OpenAlex 68
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