Stereoselective oxidation of linalool with tert-butyl hydroperoxide, catalyzed by a vanadium(V) complex with a chiral terpenoid ligand

被引:22
作者
Bryliakov, KP
Talsi, EP
Stas'ko, SN
Kholdeeva, OA
Popov, SA
Tkachev, AV
机构
[1] Boreskov Inst Catalysis, Novosibirsk 630090, Russia
[2] Novosibirsk Organ Chem Inst, Novosibirsk 630090, Russia
基金
俄罗斯基础研究基金会;
关键词
stereoselective epoxidation; linalool; terpenoid ligand; TBHP; NMR; intermediates; outer sphere complex;
D O I
10.1016/S1381-1169(02)00527-7
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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.
引用
收藏
页码:79 / 88
页数:10
相关论文
共 35 条
[31]   STRUCTURE OF THE DIMERIC ETHYLENE GLYCOL-VANADATE COMPLEX AND OTHER 1,2-DIOL-VANADATE COMPLEXES IN AQUEOUS-SOLUTION - VANADATE-BASED TRANSITION-STATE ANALOG COMPLEXES OF PHOSPHOTRANSFERASES [J].
RAY, WJ ;
CRANS, DC ;
ZHENG, J ;
BURGNER, JW ;
DENG, H ;
MAHROOFTAHIR, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (22) :6015-6026
[32]   HIGH STEREOSELECTIVITIES AND REGIOSELECTIVITIES IN TRANSITION-METAL CATALYZED EPOXIDATIONS OF OLEFINIC ALCOHOLS BY TERT-BUTYL HYDROPEROXIDE [J].
SHARPLES.KB ;
MICHAELS.RC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (18) :6136-6137
[33]  
Sharpless K.B., 1979, ALDRICHIM ACTA, V12, P63
[34]   ROLE OF VANADIUM ALKYLPEROXO COMPLEXES IN EPOXIDATION OF CYCLOHEXENE AND OXIDATION OF CYCLOHEXANE BY ORGANIC HYDROPEROXIDES IN THE PRESENCE OF BIS(ACETYLACETONATO)VANADYL [J].
TALSI, EP ;
CHINAKOV, VD ;
BABENKO, VP ;
ZAMARAEV, KI .
JOURNAL OF MOLECULAR CATALYSIS, 1993, 81 (02) :235-254
[35]  
ZAMARAEV K, 1994, NEW J CHEM, V18, P3