Stereoselective oxidation of linalool with tert-butyl hydroperoxide, catalyzed by a vanadium(V) complex with a chiral terpenoid ligand Full article
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Journal of Molecular Catalysis A: Chemical
ISSN: 1381-1169 |
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| Output data | Year: 2003, Volume: 194, Number: 1-2, Article number : PII S1381-1169(02)00527-7, Pages count : 10 DOI: 10.1016/S1381-1169(02)00527-7 | ||||
| Tags | stereoselective epoxidation; linalool; terpenoid ligand; TBHP; NMR; intermediates; outer sphere complex | ||||
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Abstract:
Stereoselective epoxidation of (-)-(R)-linalool by tert-butylhydroperoxide (TBHP) catalyzed by a vanadium(V) complex formed by interaction of [VO(acac)(2)] or [VO(On-Bu)(3)] with a new chiral terpenoid ligand (L) is reported. Moderate diastereomeric excess (de 56%) was attained in toluene at 20 degreesC. V-51, C-13 and O-17 NMR spectroscopic monitoring of the studied catalytic system showed that a new complex 1 forms quantitatively upon interaction of [VO(On-Bu)(3)] with L in CH2O2. Compound 1 is a mononuclear complex of vanadium(V), which incorporates the tridentate chiral ligand L, as well as V=O moieties. It has been shown that TBHP binds to 1 giving a 1.TBHP adduct with the association constant K = 1.36 +/- 0.111 mol(-1) at room temperature and enthalpy Delta(r) H-298(0) = -6.5 +/- 2.0 kJ mol(-1) and entropy Delta(r) S-298(0) = -20 +/- 6 J mol(-1) K-1. These 29 thermodynamic parameters are typical for outer sphere complexes (OSCs). Adduct 1 .TBHP is suggested to be a precursor of the active intermediate of the stereoselective epoxidation process. (C) 2002 Elsevier Science B.V. All rights reserved.
Cite:
Bryliakov K.P.
, Talsi E.P.
, Stas'ko S.N.
, Kholdeeva O.A.
, Popov S.A.
, Tkachev A.V.
Stereoselective oxidation of linalool with tert-butyl hydroperoxide, catalyzed by a vanadium(V) complex with a chiral terpenoid ligand
Journal of Molecular Catalysis A: Chemical. 2003. V.194. N1-2. PII S1381-1169(02)00527-7 :1-10. DOI: 10.1016/S1381-1169(02)00527-7 WOS Scopus РИНЦ OpenAlex
Stereoselective oxidation of linalool with tert-butyl hydroperoxide, catalyzed by a vanadium(V) complex with a chiral terpenoid ligand
Journal of Molecular Catalysis A: Chemical. 2003. V.194. N1-2. PII S1381-1169(02)00527-7 :1-10. DOI: 10.1016/S1381-1169(02)00527-7 WOS Scopus РИНЦ OpenAlex
Dates:
| Published print: | Mar 1, 2003 |
Identifiers:
| Web of science: | WOS:000181555200009 |
| Scopus: | 2-s2.0-0037416061 |
| Elibrary: | 13428479 |
| OpenAlex: | W2044715656 |