Solvent-free Ru-catalyzed isomerization of allyloxyalcohols: Methods for highly selective synthesis of 1-propenyloxyalcohols
PBN-AR
Instytucja
Wydział Matematyki, Fizyki i Chemii (Uniwersytet Śląski w Katowicach)
Informacje podstawowe
Główny język publikacji
EN
Czasopismo
APPLIED CATALYSIS A-GENERAL
ISSN
0926-860X
EISSN
Wydawca
ELSEVIER SCIENCE BV
DOI
URL
Rok publikacji
2013
Numer zeszytu
Strony od-do
101-111
Numer tomu
451
Identyfikator DOI
Liczba arkuszy
0,5
Autorzy
Pozostali autorzy
+ 3
Słowa kluczowe
EN
1-Propenyl ethers
Allyl ethers
Isomerization
Ruthenium complexes
Vinyl ethers
Streszczenia
Język
EN
Treść
An excellent, selective and very convenient method for the synthesis of hydroxyalkyl vinyl ethers of HO–A–O–CHdouble bond; length as m-dashCHCH3 type via isomerization of appropriate readily available allylic substrate of HO–A–O–CH2CHdouble bond; length as m-dashCH2 type mediated by various soluble ruthenium complexes under solvent-free conditions has been presented. Our research has demonstrated that (CH2)n or (CH2CH2O)n or ortho-phenylene, but neither –CH2Ctriple bond; length of mdashCCH2– nor –CH2CHdouble bond; length as m-dashCHCH2– can play a role of an A linker. The use of detailed screening experiments allowed discovering new, efficient catalysts for a highly selective isomerization of allyloxyalcohols such as [RuH2(CO)(PPh3)3], [RuH2(PPh3)4] or [Ru(CO)3(PPh3)2]. For these ruthenium complexes, the only reaction products were enol ethers, and an intra- and/or intermolecular addition of an OH group to the double bond has not been observed. The use of the complexes containing Cl ligand as catalysts precursors ([RuClH(CO)(PPh3)3], [RuCl2(PPh3)3], RuCl3·3H2O and other) and surprisingly also [Ru3(CO)12] led to a consequent cyclization and/or polymerization of enol ethers. The addition to the catalytic system of trialkyl amines, K2CO3, CaH2 and others as scavengers of HCl (generated in situ from Ru–Cl complexes) has also allowed to eliminate fully consequent reactions. The scale-up of the selected method of isomerization has been successfully performed and the best results were obtained for [RuH2(CO)(PPh3)3] and [RuCl2(PPh3)3] + 5 K2CO3. Finally, several pathways of the reaction between allyloxyalcohols and the ruthenium complexes of various structures have been proposed. The double bond migration and addition of the OH group to the allyl or the vinyl ether moiety could proceed according to the transition metal catalysis mechanisms and tandems the transition metal catalysis-Lewis acid catalysis or the transition metal catalysis-Brønsted acid catalysis.
Inne
System-identifier
0192400096704
CrossrefMetadata from Crossref logo
Cytowania
Liczba prac cytujących tę pracę
Brak danych
Referencje
Liczba prac cytowanych przez tę pracę
Brak danych