6849-18-9Relevant academic research and scientific papers
Palladium-catalyzed alkoxycarbonylation of conjugated dienes under acid-free conditions: Atom-economic synthesis of β,γ-unsaturated esters
Fang, Xianjie,Li, Haoquan,Jackstell, Ralf,Beller, Matthias
supporting information, p. 9030 - 9034 (2014/09/17)
Carbonylation reactions constitute important methodologies for the synthesis of all kinds of carboxylic acid derivatives. The development of novel and better catalysts for these transformations is of interest for both academic and industrial research. Here, a benign palladium-based catalyst system for the alkoxycarbonylation of conjugated dienes under acid-free conditions has been developed. This atom-efficient transformation provides straightforward access to a variety of β,γ-unsaturated esters in good to excellent yields and often with high selectivities. As an industrially relevant example the (formal) synthesis of dimethyl adipate and ε-caprolactam from 1,3-butadiene is demonstrated.
A Convenient Route to β,γ-Unsaturated Esters without Formation of the α,β-Isomers. Palladium-Catalyzed Alkoxycarbonylation of Allylic Halides under Alcohol-Potassium Carbonate Tow-Phase Conditions
Kiji, Jitsuo,Okano, Tamon,Higashimae, Yukiko,Fukui, Yasuyuki
, p. 1029 - 1031 (2007/10/03)
Palladium-catalyzed, atmospheric pressure carbonylation of allylic halides under alcohol-potassium carbonate (liquid-solid) two-phase conditions affords β,γ-unsaturated esters without formation of the α,β-isomers. Phosphine-free palladium compounds such a
Selective hydrogenation of simple and functionalized conjugated dienes using a binuclear palladium complex catalyst precursor
Cho, In Sik,Alper, Howard
, p. 5673 - 5676 (2007/10/02)
The selective 1,2-hydrogenation of simple and functionalized conjugated dienes is catalyzed by preactivation of the binuclear palladium complex, [(Bu(t)2PH)PdPBu(t)2]2 with oxygen, in THF at room temperature and 1 atm of hydrogen pressure, to form monoenes in excellent yield.
Direct Conversion of β,γ-Unsaturated Esters into Lactones Induced by TMS-I
Piva, Olivier
, p. 13687 - 13696 (2007/10/02)
β,γ-unsaturated esters readily prepared by photodeconjugation are converted in one step into butanolides by treatment with TMS-I.The reaction has been extended to the access to α-alkylidene lactones.
SYNTHESIS WITH MANGANIC SALTS; PART III: SYNTHESIS OF 1,4-DIKETONES THROUGH MANGANIC ACETATE-MEDIATED ADDITION OF KETONE TO ISOPENTENYL SULFONES. ACETOXYLATION OF Β,Γ-UNSATURATED KETONES BY MANGANOUS AND CUPRIC ACETATES
Breuilles, Pascal,Uguen, Daniel
, p. 705 - 720 (2007/10/02)
Conditions have been found to selectively add ketones to isopentenyl sulfones.The major product, a ketone bearing a methylene group at the γ position, gave upon ozonolysis the corresponding 1,4-diketone.The usefulness of the overall process was illustrated by the efficient syntheses of jasmone and of one half of pyrenophorine.The γ-acetoxy conjugated enones that invariably formed during these additions resulted from the oxidation of an isomeric β,γ-unsaturated ketone by manganous and cupric acetates.Such an acetoxylation has been used to prepare 6β-acetoxy-cholestenone from cholesterol and also to prepare chrysanthemic acid.
Equilibration of 5-Methyl-3-hexen-2-one and 5-Methyl-3-hexen-2-one and of XCH2CH=CYZ/XCH=CHCHYZ Pairs in General
Hine, Jack,Linden, Shwn-Meei
, p. 584 - 587 (2007/10/02)
The equilibrium constant for isomerization of 5-methyl-4-hexen-2-one to trans-5-methyl-3-hexen-2-one in tert-butyl alcohol at 25 deg C has been found to be 0.40, which is smaller by 250-fold than a literature value.This and other equilibrium constants for reactions of the type XCH2CH=CMe2 XCH=CHCHME2 are shown to be consistent with the double bond stabilizing abilities of various groups as measured by equilibrium constants for reactions of the type XCH2CH=CHY XCH=CHCH2Y.The general case of isomerizations of the type XCH2CH=CYZ XCH=CHCHYZ is also discussed.
