74244-64-7Relevant articles and documents
APPLICATION OF OLEFIN METATHESIS TO ORGANIC SYNTHESIS. SYNTHESES OF CIVETONE AND MACROLIDES
Tsuji, Jiro,Hashiguchi, Shohei
, p. 2955 - 2958 (1980)
Diethyl 9-octadecene-1,18-dioate was obtained in 87percent yield based on 50percent theoretical conversion by the olefin metathesis reaction catalyzed by WOCl4-Cp2TiMe2.The Dieckmann condensation of this diester using potassium hydride afforded 2-ethoxycarbonylcyclo-9-heptadecenone, which was converted by hydrolysis and decarboxylation to cyclo-9-heptadecenone (civetone) as a mixture of cis and trans isomers (1.3 : 1) in 54percent yield.Also 9-octadecen-18-olide was obtained in 17.9percent by the metathesis of oleyl oleate.
At Long Last: Olefin Metathesis Macrocyclization at High Concentration
Sytniczuk, Adrian,Dabrowski, Micha?,Banach, ?ukasz,Urban, Mateusz,Czarnocka-?niada?a, Sylwia,Milewski, Mariusz,Kajetanowicz, Anna,Grela, Karol
supporting information, p. 8895 - 8901 (2018/07/05)
Macrocyclic lactones, ketones, and ethers can be obtained in the High-Concentration Ring-Closing Metathesis (HC-RCM) reaction in high yield and selectivity at concentrations 40 to 380 times higher than those typically used by organic chemists for similar macrocyclizations. The new method consists of using tailored ruthenium catalysts together with applying vacuum to distill off the macrocyclic product as it is formed by the metathetical backbiting of oligomers. Unlike classical RCM, no large quantities of organic solvents are used, but rather inexpensive nonvolatile diluents, such as natural or synthetic paraffin oils. Moreover, use of a protecting atmosphere or a glovebox is not needed, as the new catalysts are perfectly moisture and air stable. In addition, some other cyclic compounds previously reported as unobtainable by RCM in neat conditions, or in high dilutions even, can be formed with the help of the HC-RCM method.
METATHESIS REACTIONS OF UNSATURATED ESTERS CATALYZED BY HOMOGENEOUS TUNGSTEN COMPLEXES. SYNTHESES OF CIVETONE AND MACROLIDES
Tsuji, Jiro,Hashiguchi, Shohei
, p. 69 - 80 (2007/10/02)
The metathesis reactions of methyl 10-undecenoate, methyl oleate and oleyl acetate have been carried out using WCl6 and WOCl4 as primary catalysts and SnMe4, PbMe4, Cp2TiMe2, and Cp2ZrMe2 as cocatalysts.The catalyst system WOCl4/Cp2TiMe2 was found to be very active for the metathesis of the unsaturated esters and is somewhat better than the system WCl6/SnMe4.Diethyl 9-octadecene-1,18-dioate, obtained by the metathesis of ethyl oleate, was subjected to the Dieckmann cyclization.The cyclized product was decarboxylated to give civetone as a mixture of the cis and trans isomers.Preliminary studies of macrolide synthesis by the intramolecular metathesis of oleyl oleate and 10-undecenyl 10-undecenoate to afford 9-octadecen-18-olide and 10-eicosen-20-olide, respectively, have been carried out.
