Multinuclear NMR Study of the Reactive Intermediates in Enantioselective Epoxidations of Allylic Alcohols Catalyzed by a Vanadium Complex Derived from a Planar-Chiral Hydroxamic Acid Научная публикация
| Журнал |
New Journal of Chemistry
ISSN: 1144-0546 , E-ISSN: 1369-9261 |
||||
|---|---|---|---|---|---|
| Вых. Данные | Год: 2003, Том: 27, Номер: 3, Страницы: 609-614 Страниц : 6 DOI: 10.1039/b208748k | ||||
| Ключевые слова | allyl alcohol; carbon 13; epoxide; geraniol; hydroxamic acid; metal complex; oxygen 17; paracyclophane derivative; tert butyl hydroperoxide; vanadium derivative | ||||
| Авторы |
|
||||
| Организации |
|
Информация о финансировании (4)
| 1 | Российский фонд фундаментальных исследований | 00-03-32438 |
| 2 | International Association for the Promotion of Co-operation with Scientists from the New Independent States of the Former Soviet Union | YSF-006 |
| 3 | German Research Foundation | |
| 4 | Verband der Chemischen Industrie |
Реферат:
Structure and reactivity of vanadium(V) complexes formed in situ in the catalytic system VO(Oalkyl)3/hydroxamic acid/tert-butylhydroperoxide (TBHP) have been examined by means of 51V, 13C and 17O NMR spectroscopy. For the first time, reactive vanadium(V) alkylperoxo intermediates in vanadium/hydroxamic acid epoxidations were observed and spectroscopically characterized. With a planar-chiral [2.2]paracyclophane-derived hydroxamate as ligand two diastereomeric alkylperoxo vanadium(V) complexes were formed in a 3∶1 ratio. They differ in the relative positioning of the V[double bond, length as m-dash]O group and the planar-chiral aromatic part. Upon addition of geraniol as substrate, these complexes disappear in a parallel manner, and geraniol epoxide is formed. Probably, the existence of these two diastereomeric complexes and their comparable reactivity account for the observed enantioselectivity level (≤71% ee) and hence sets a fundamental limitation for the use of such ligands in this asymmetric catalysis.
Библиографическая ссылка:
Bryliakov K.P.
, Talsi E.P.
, Kühn T.
, Bolm C.
Multinuclear NMR Study of the Reactive Intermediates in Enantioselective Epoxidations of Allylic Alcohols Catalyzed by a Vanadium Complex Derived from a Planar-Chiral Hydroxamic Acid
New Journal of Chemistry. 2003. V.27. N3. P.609-614. DOI: 10.1039/b208748k WOS Scopus РИНЦ CAPlusCA OpenAlex
Multinuclear NMR Study of the Reactive Intermediates in Enantioselective Epoxidations of Allylic Alcohols Catalyzed by a Vanadium Complex Derived from a Planar-Chiral Hydroxamic Acid
New Journal of Chemistry. 2003. V.27. N3. P.609-614. DOI: 10.1039/b208748k WOS Scopus РИНЦ CAPlusCA OpenAlex
Даты:
| Поступила в редакцию: | 4 сент. 2002 г. |
| Принята к публикации: | 5 нояб. 2002 г. |
| Опубликована online: | 15 янв. 2003 г. |
| Опубликована в печати: | 27 февр. 2003 г. |
Идентификаторы БД:
| Web of science: | WOS:000181210200028 |
| Scopus: | 2-s2.0-0037352252 |
| РИНЦ: | 13426818 |
| Chemical Abstracts: | 2003:149731 |
| Chemical Abstracts (print): | 139:117495 |
| OpenAlex: | W2041465935 |