Highly Enantioselective C−H Oxidation of Arylalkanes with H2O2 in the Presence of Chiral Mn-Aminopyridine Complexes Full article
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ChemCatChem
ISSN: 1867-3880 , E-ISSN: 1867-3899 |
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| Output data | Year: 2017, Volume: 9, Number: 24, Pages: 4580-4586 Pages count : 7 DOI: 10.1002/cctc.201701169 | ||||||
| Tags | asymmetric catalysis, C−H hydroxylation, enzyme models, hydrogen peroxide, manganese | ||||||
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Funding (1)
| 1 | Russian Science Foundation | 17-13-01117 |
Abstract:
Bioinspired chiral Mn-aminopyridine complexes [(S,S)-LMnII(OTf)2] and [(R,R)-LMnII(OTf)2] (where (S,S)-L=(2S,2′S)-1,1′-bis((3-methyl-4-(2,2,2-trifluoroethoxy)pyridin-2-yl)methyl)-2,2′-bipyrrolidine, and (R,R)-L=(2R,2′R)-1,1′-bis((3-methyl-4-(2,2,2-trifluoroethoxy)pyridin-2-yl)methyl)-2,2′-bipyrrolidine) have been shown to efficiently catalyze the benzylic C−H oxidation of arylalkanes with hydrogen peroxide in the presence of carboxylic acid additives, affording enantiomerically enriched 1-arylalkanols and the corresponding ketones. Optically pure additive N-Boc-(L)-proline, in combination with [(R,R)-LMnII(OTf)2] complex, affords 1-arylalkanols in up to 86 % ee, which is the highest reported enantioselectivity for direct benzylic hydroxylations with H2O2 in the presence of transition-metal catalysts. Oxidative kinetic resolution only slightly contributes to the increase of the observed enantiomeric excess over the reaction course. The observed kH/kD values (3.5–3.6 for the oxidation of ethylbenzene/d10-ethylbenzene) and competitive oxidation data are consistent with either a hydrogen-atom transfer/oxygen rebound or hydride transfer/oxygen rebound asymmetric hydroxylation mechanism.
Cite:
Talsi E.P.
, Samsonenko D.G.
, Ottenbacher R.V.
, Bryliakov K.P.
Highly Enantioselective C−H Oxidation of Arylalkanes with H2O2 in the Presence of Chiral Mn-Aminopyridine Complexes
ChemCatChem. 2017. V.9. N24. P.4580-4586. DOI: 10.1002/cctc.201701169 WOS Scopus РИНЦ ANCAN OpenAlex
Highly Enantioselective C−H Oxidation of Arylalkanes with H2O2 in the Presence of Chiral Mn-Aminopyridine Complexes
ChemCatChem. 2017. V.9. N24. P.4580-4586. DOI: 10.1002/cctc.201701169 WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
| Submitted: | Jul 18, 2017 |
| Published online: | Aug 10, 2017 |
| Published print: | Dec 20, 2017 |
Identifiers:
| Web of science: | WOS:000418390700018 |
| Scopus: | 2-s2.0-85029396833 |
| Elibrary: | 35479178 |
| Chemical Abstracts: | 2017:1869643 |
| Chemical Abstracts (print): | 168:46187 |
| OpenAlex: | W2744584509 |