Stereoselective Oxidation of Linalool with tert-Butyl Hydroperoxide, Catalyzed by a Vanadium(V) Complex with a Chiral Terpenoid Ligand Научная публикация
| Журнал |
Journal of Molecular Catalysis A: Chemical
ISSN: 1381-1169 |
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| Вых. Данные | Год: 2003, Том: 194, Номер: 1-2, Страницы: 79-88 Страниц : 10 DOI: 10.1016/S1381-1169(02)00527-7 | ||||
| Ключевые слова | Intermediates, Linalool, NMR, Outer sphere complex, Stereoselective epoxidation, TBHP, Terpenoid ligand | ||||
| Авторы |
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| Организации |
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Информация о финансировании (1)
| 1 | Российский фонд фундаментальных исследований | 00-03-32438 |
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 °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 VO 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.
Библиографическая ссылка:
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 CAPlusCA 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. P.79-88. DOI: 10.1016/S1381-1169(02)00527-7 WOS Scopus РИНЦ CAPlusCA OpenAlex
Даты:
| Поступила в редакцию: | 5 сент. 2002 г. |
| Принята к публикации: | 5 сент. 2002 г. |
| Опубликована online: | 5 дек. 2002 г. |
| Опубликована в печати: | 3 мар. 2003 г. |
Идентификаторы БД:
| Web of science: | WOS:000181555200009 |
| Scopus: | 2-s2.0-0037416061 |
| РИНЦ: | 13428479 |
| Chemical Abstracts: | 2003:162105 |
| Chemical Abstracts (print): | 139:54513 |
| OpenAlex: | W2044715656 |