Реферат: 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.

Библиографическая ссылка: 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

Даты:

Опубликована в печати:

1 мар. 2003 г.

Идентификаторы:

Web of science	WOS:000181555200009
Scopus	2-s2.0-0037416061
РИНЦ	13428479
OpenAlex	W2044715656

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