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 °C. Full-size image (<1 K), Full-size image (<1 K) and Full-size image (<1 K) 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 CH2Cl2. 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±0.11 l mol−1 at room temperature and enthalpy ΔrH2980=−6.5±2.0 kJ mol−1 and entropy ΔrS2980=−20±6 J mol−1 K−1. These 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.

Cite: Bryliakov K.P. , Talsi E.P. , Stasʹko 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. P.79-88. DOI: 10.1016/S1381-1169(02)00527-7 WOS Scopus РИНЦ ANCAN OpenAlex

Dates:

Submitted:	Sep 5, 2002
Accepted:	Sep 5, 2002
Published online:	Dec 5, 2002
Published print:	Mar 3, 2003

Identifiers:

Web of science:	WOS:000181555200009
Scopus:	2-s2.0-0037416061
Elibrary:	13428479
Chemical Abstracts:	2003:162105
Chemical Abstracts (print):	139:54513
OpenAlex:	W2044715656

Citing:

DB	Citing
Web of science	23
Scopus	24
Elibrary	26
OpenAlex	26

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