19894-79-2Relevant articles and documents
Neryl- and geranyltriethylammonium halides in the allylation of sodium diethyl malonate. The effect of the leaving group of the allylating reagent on the selectivity of the reaction
Petrushkina, E. A.,Zakharkin, L. I.
, p. 249 - 251 (1994)
In the absence of catalyst, N-neryl- and N-geranyltriethylammonium halides can allylate sodium ethyl malonate to give terpene malonate derivatives.Using the above-mentioned amonium salts, geranyl and neryl acetates, geranyl ethyl carbonate, and geranyl diethyl phosphate as examples, it has been shown that with Pd0 and PdII catalysts, the selectivity of formation of neryl-, geranyl-, and linalylmalonates can be governed by varying the leaving group of the allylating agent. - Key words: palladium, complexes, catalysis, sodium diethyl malonate, allylation.
Experimental and theoretical studies on the bismuth-triflate-catalysed cycloisomerisation of 1,6,10-trienes and aryl polyenes
Godeau, Julien,Fontaine-Vive, Fabien,Antoniotti, Sylvain,Du?ach, Elisabet
supporting information, p. 16815 - 16822 (2013/03/28)
Cycloisomerisation of polyenes such as diethyl geranylprenylmalonate [(E)-1 a], diethyl geranylphenylmalonate [(E)-2 a] and diethyl cinnamylgeranylmalonate [(E,E)-3 a] catalysed by bismuth triflate was studied from experimental and theoretical viewpoints. Several intermediates were isolated and characterised, and calculated transition-state structures are proposed for the three reactions. The diastereoselectivity observed during the reaction of (E)- or (Z)-2 a in favour of the formation of trans-fused bicyclic products is discussed in detail. The nature of the active catalytic species derived from bismuth triflate was also investigated, and the formation of a hybrid Lewis acid/Br?nsted acid catalyst with water molecules is proposed, supported by experimental and theoretical data. Round and round: Cycloisomerisation reaction mechanisms involving polyenes and aryl trienes catalysed by bismuth triflate were studied experimentally and theoretically. The diastereoselectivity observed during the reaction of E or Z olefins in favour of trans-fused bicyclic products is discussed. The nature of the active catalytic species derived from bismuth triflate was also investigated, and formation of a hybrid Lewis acid/Br?nsted acid catalyst with water molecules is proposed (see figure). Copyright
Synthesis of derivatives of prenylacetic acids by reactions of alkyl malonate, cyanoacetate, and acetoacetate with alkylating reagents in ionic liquids
Kryshtal,Zhdankina,Zlotin
, p. 652 - 658 (2007/10/03)
A method for the synthesis of carboxylic acid derivatives containing one or two - CH2CHn(Me)CHn+1CH2 - fragments (n = 0, 1) was developed. The method is based on the alkylation of (di)alkyl malonates, cyanoacetates, and acetoacetates with acyclic prenyl halides in ionic liquids, 1-butyl-3-methylimidazolium hexafluorophosphate and tetrafluoroborate. For the ambident ethyl acetoacetate anion, the reactions with prenyl halides devoid of a double bond in the allylic position relative to the halogen atom carried out in the ionic liquids give mixtures of C- and O-alkylation products, while in the case of allylic prenyl halides, only C-alkylation products are formed. The reactions of ethyl 2-geranylmalonate and 2-geranylacetoacetate with bromocyclohexane and 1-chloro-3-dimethylaminopropane in ionic liquids provided derivatives of pharmacologically active geranylacetic acids. The product yields are higher than those in molecular organic solvents. The ionic liquids were recovered and reused in the alkylation.
Method for lowering cholesterol employing a phosphonomethylphosphinate squalene synthetase inhibitor
-
, (2008/06/13)
A method is provided for inhibiting cholesterol biosynthesis by inhibiting de novo squalene production employing methylene phosphonoalkylphosphinate compounds.
