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
Biomimetic cationic polyannulation reaction catalyzed by Bi(OTf) 3: Cyclization of 1,6-dienes, 1,6,10-trienes, and aryl polyenes
Godeau, Julien,Olivero, Sandra,Antoniotti, Sylvain,Dunach, Elisabet
supporting information; experimental part, p. 3320 - 3323 (2011/09/15)
Nonactivated trienes and aryltrienes were cyclized into polycyclic compounds in good to excellent yields under bismuth triflate catalysis in a biomimetic fashion. The reaction showed broad applicability and allowed for the formation of functionalized bicyclic to tetracyclic structures from simple precursors in one pot. For some specific substrates, the cyclization was followed by a methyl shift as encountered in terpenoid biosynthesis.
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.
Et3B-promoted, Pd(0)-catalyzed allylation of active methylene compounds with allylic alcohols
Tamaru, Yoshinao,Horino, Yoshikazu,Araki, Misato,Tanaka, Shuji,Kimura, Masanari
, p. 5705 - 5709 (2007/10/03)
Triethylborane promotes the Pd(0)-catalyzed allylation of active methylene compounds (Meldrum's acid and malonates) with a variety of allylic alcohols. The reaction proceeds smoothly at room temperature and provides the allylation products in good yield. (C) 2000 Elsevier Science Ltd.
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.
Methods of using α-phosphonosulfonate squalene synthetase inhibitors including the treatment of atherosclerosis and hypercholesterolemia
-
, (2008/06/13)
α-Phosphonosulfonate compounds are provided which inhibit the enzyme squalene synthetase and thereby inhibit cholesterol biosynthesis. These compounds have the formula STR1 wherein R2 is OR5 or R5a ; R3 and R5 are independently H, alkyl, arylalkyl, aryl or cycloalkyl; R5a is H, alkyl, arylalkyl or aryl; R4 is H, alkyl, aryl, arylalkyl, or cycloalkyl;, Z is H, halogen, lower alkyl or lower alkenyl; and R1 is a lipophilic group which contains at least 7 carbons and is alkyl, alkenyl, alkynyl, mixed alkenyl-alkynyl, aryl, arylalkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl, cycloheteroalkyl, cycloheteroalkylalkyl; as further defined above; including pharmaceutically acceptable salts and or prodrug esters of the phosphonic (phosphinic) and/or sulfonic acids.
α-phosphonocarboxylate squalene synthetase inhibitors
-
, (2008/06/13)
α- Phosphonocarboxylate compounds are provided which inhibit the enzyme squalene synthetase and thereby inhibit cholesterol biosynthesis. These compounds have the formula STR1 wherein R1 is a lipophilic group which contains at least 7 carbons and is substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkylalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted arylalkyl or optionally substituted aryl; Z is H, halogen, hydroxy, hydroxyalkyl or lower alkyl; R2 and R3 are independently H, metal ion or other pharmaceutically acceptable cation, or a prodrug ester; R4 is H, metal ion or other pharmaceutically acceptable cation, lower alkyl, lower alkenyl, arylalkyl, aryl or a prodrug ester.
Palladium(0)-Catalyzed Allylic Substitution with Allylic Alkoxides as Substrates
Stary, Ivo,Stara, Irena G.,Kocovsky, Pavel
, p. 529 - 538 (2007/10/02)
A new method has been developed which allows palladium(0)-cayalyzed allylic substitution to occur between allylic alcohols and anionic C-nucleophiles: on reaction with Ph3B, the allylic alkoxide 2 is first converted in situ into the more reactive species 3 which then undergoes a Pd(0)-catalyzed reaction with lithio diethyl malonate via the η3-complex 6.Allylic alkoxides can be generated in situ either by deprotonation of the corresponding alcohol (1 -> 2, e.g. with BuLi), via a vinylmagnesium haalide addition to the corresponding aldehyde (4 + 5 -> 2), or by hydride reduction (DIBAH) of α,β-unsaturated ketones (31 -> 32).The whole sequence can be carried out as a one pot procedure and is suitable for sensitive allylic alcohols that might be difficult to handle in pure state.While primary allylic alcohols (7 and 18) and their allylic isomers (14 and 15) give mixtures of mono- and bis-allylated products with LiCH(CO2Et)2, exclusive monoallylation has been observed for secondary alcohols (21, 23, and 26).
Hydroxyphosphinyl phosphonate squalene synthetase inhibitors and method
-
, (2008/06/13)
Hydroxyphosphinyl phosphonate compounds are provided which inhibit the enzyme squalene synthetase and thereby inhibit cholesterol biosynthesis. These compounds have the formula STR1 wherein R2, R3 and R4 are independently H, alkyl, metal ion or a prodrug ester; and R1 is a lipophilic group which contains at least 6 carbons and is alkyl, alkenyl, alkynyl, mixed alkenylalkynyl, a hetero-containing moiety as defined herein, or a phenylalkyl or phenylalkenyl group including those containing a biphenyl group.
