758-66-7Relevant academic research and scientific papers
Palladium-catalyzed allylation of malonic acid derivatives in heterogeneous systems containing ionic liquids
Vasil'ev, Andrei A.,Zlotin, Sergei G.
, p. 23 - 25 (2014/02/14)
Palladium-catalyzed potassium carbonate-assisted reaction between diethyl malonate and allyl acetate in the presence of 1,3-dialkyl-imidazolium ionic liquids (ILs) as solvents or phase transfer catalysts affords major monoallylation product, whereas in the presence of 1,2,3-trialkylimidazolium or quaternary ammonium/phosphonium ILs diallylation product is preferably formed. These procedures are extended to some other CH-acids and allylic acetates.
Pd-catalyzed allylation of CH acids under phase-transfer conditions
Vasil’ev,Lyubimov,Serebryakov,Davankov,Struchkova,Zlotin
experimental part, p. 605 - 610 (2011/02/17)
The composition of the products obtained by Pd-catalyzed allylation of diethyl (alkyl)- malonates and ethyl cyanoacetate with allylic acetates under phase-transfer conditions using potassium carbonate or phosphate as bases depended strongly on the nature of the reactants and the ligands used. The highest yields and the fraction of the "linear" regioisomers were achieved in the reactions of prenyl or 3-methylbut-1-en-3-yl acetates in the presence of phosphordiamidite ligands.
Regioselective palladium-catalysed prenylation of CH acids in the presence of diamidophosphite ligands and potassium carbonate
Vasil'ev, Andrei A.,Lyubimov, Sergey E.,Serebryakov, Edward P.,Davankov, Vadim A.,Zlotin, Sergei G.
scheme or table, p. 103 - 105 (2009/06/08)
The palladium-catalysed prenylation of CH acids with 3-methylbut-1-en-3-yl or prenyl acetates under phase-transfer conditions affords high yield of the linear regioisomer provided by the use of diamidophosphite ligands.
Iridium complex-catalyzed allylic alkylation of allylic esters and allylic alcohols: Unique regio- and stereoselectivity
Takeuchi, Ryo,Kashio, Mikihiro
, p. 8647 - 8655 (2007/10/03)
An iridium complex was found to be an efficient catalyst for allylic alkylation of allylic esters with a stabilized carbon nucleophile. Highly regioselective alkylation at the substituted allylic terminus was achieved. The catalytic activity and regioselectivity were affected by the ligand used. The reaction of (E)-2-alkenyl acetates or 1-substituted 2-propeny acetates with dialkyl sodiomalonate in the presence of a catalytic amount of [Ir(COD)Cl]2/P(OPh)3 (P/Ir = 1-2) gave a product alkylated at the substituted allylic terminus in 95-99% selectivity. Construction of a quaternary carbon center is possible by this methodology. The reaction of 1,1-dialkyl-2-propenyl acetates gave a product alkylated at the disubstituted allylic terminus exclusively. (E)-2-Alken-1-ol could be successfully used as a substrate. The products alkylated at the substituted allylic terminus were obtained in 93-99% selectivity. A 31P NMR study of the reaction of [Ir(COD)Cl]2 with P(OPh)3 revealed that a catalytically active species is a monophosphite species. The π-acceptor property of P(OPh)3 promotes a carbonium ion character at the substituted allylic terminus and directs the nucleophilic attack to this position. The stereochemistry of the allyl system affected the regioselectivity. In contrast to the reaction of (E)-2-alkenyl acetates, the reaction of (Z)-2-alkenyl acetates gave a product alkylated at the unsubstituted allylic terminus predominantly. This shows that the regioselectivity of the alkylation of the syn π-allyl iridium intermediate is different from that of the anti π-allyl iridium intermediate. (Z)- Selective allylic alkylation of (Z)-2-alkenyl esters is also possible by iridium catalysis.
Highly selective allylic alkylation with a carbon nucleophile at the more substituted allylic terminus catalyzed by an iridium complex: An efficient method for constructing quaternary carbon centers
Takeuchi,Kashio
, p. 263 - 265 (2007/10/03)
The selective construction of quaternary carbon centers, which are frequently found in natural products, is essential to many syntheses. A new method relying on the iridium complex [Ir(cod)Cl]2 as the catalyst can be used for the allylic alkylation of acyclic compounds 1. The products are obtained in yields between 70 and 85% and with a selectivity of 100%, cod = cyclooctadiene.
Allylation of Active Methylene Compounds with Allyl Oxime Carbonates Catalyzed by Pd(0)
Suzuki, Osamu,Hashiguchi, Yoshiharu,Inoue, Seiichi,Sato, Kikumasa
, p. 291 - 294 (2007/10/02)
Allylation of active methylene compounds catalyzed by a palladium(0)-phosphine system took place highly stereoselectively by employing allyl oxime carbonates as the allylating reagent.
Etude de l'allylation, catalysee par le nickel, d'enolates stables, par les ethers et les alcools allyliques
Alvarez, Eleuterio,Cuvigny, Therese,Julia, Marc
, p. 199 - 212 (2007/10/02)
The allylation of stable enolates derived from diethyl malonate and ethyl cyanoacetate by a variety of aliphatic or aromatic allylic ethers and by allylic alcohols, under nickel catalysis, was investigated.The influence of ligands, solvents and temperature was studied.
On the Regio- and Stereoselectivity of Bu4N-Catalyzed Allylic Alkylation
Xu, Yuanyao,Zhou, Bo
, p. 974 - 977 (2007/10/02)
Bu4N has been found to catalyze the alkylation of allylic carbonate with malonate anion.The reaction proceeds with good regioselectivity, the nucleophile attacking predominantly at the carbon where the leaving group was attached.Retention of configuration of the double bond during the course of reaction was observed.Alkylation of methyl (Z)-5-carbomethoxy-1-cyclohexen-3-yl carbonate with sodium salt of dimethyl malonate yielded dimethyl ((Z)-5-carbomethoxy-1-cyclohexen-3-yl)malonate in a highly stereoselective fashion, and a net retention of configuration at the center undergoing substitution is thus established.On the basis of regio- and stereochemical results, a reaction pathway involving an ?-allyliron complex has been suggested.
SUBSTITUTIONS CATALYSEES AU NICKEL D'ACETATES ET DE SULFONES ALLYLIQUES
Cuvigny, Therese,Julia, Marc
, p. 383 - 408 (2007/10/02)
The allylic substitution of stable enolates derived from diethyl malonate, ethyl cyanoacetate, ethyl benzylsulfonylacetate, bis(benzenesulfonyl)methane and sodium p-toluenesulfinate by a variety of allylic esters and sulfones has been investigated.Suitable ligands and reaction conditions have been found to ensure high yields, and in some cases considerable control of the regioselectivity of the reaction.
ETUDE DE LA REGIOSELECTIVITE DE LA SUBSTITUTION DES CARBANIONS PAR DES DERIVATIVES ALLIQUES CATALYSEE AU PALLADIUM. OBTENTION SELECTIVE DE COMPOSES A CARBONE QUATERNAIRE
Cuvigny, Therese,Julia, Marc,Rolando, C.
, p. 395 - 414 (2007/10/02)
The influence of the leaving groups, carbanions and ligands on ?-allylpalladium has been investigated in the substitution of primary or tertiary terpene derivatives.Conditions have been found under which the substitution takes place essentially at one or the other end of the allylic system.This provides a new and convenient way to obtain compounds with quaternary carbon atoms, which has been exemplified by the synthesis of 3,3-dimethyl-4-pentenenitrile.
