Methods of making olefinic e- and z-isomers

Abstract

Method of making a second olefm using a first olefin, comprising steps (A) and (B): (A) performing a metathesis reaction with the first olefm in the presence of a metal complex configured to catalyse said metathesis reaction; (B) epoxidizing an olefin contained in the reaction mixture obtained in step (A) to form an epoxide; and deoxygenizing said epoxide to form said second olefin.

1 - 20 . (canceled) 
     
     
         21 . A method of making a second olefin using a first olefin, comprising steps (A) and (B):
 (A) performing a metathesis reaction with the first olefin in the presence of a metal complex configured to catalyse said metathesis reaction in order to obtain a reaction mixture containing an olefin;   (B) epoxidizing the olefin contained in the reaction mixture obtained in step (A) to form an epoxide; and deoxygenizing said epoxide to form said second olefin;   wherein step (A) comprises step (Al 1):   (A11) subjecting the first olefin to a cross metathesis reaction with a fourth olefin in the presence of a metal complex to form a fifth olefin, wherein the metal complex is configured to favour the formation of the Z-isomer over the formation of the E-isomer of the fifth olefin;   and further comprising the subsequent conversion of the Z-isomer into the E-isomer to form the second olefin, wherein step (B) comprises steps (B11) to (B14):   (B11) epoxidizing said Z-isomer;   (B12) subjecting the epoxide obtained in step (B11) to hydrolysis to form a diol or to alcoholysis to form a beta-hydroxy ether;   (B13) converting the diol or beta-hydroxy ether obtained in step (B12) to a 1,3-dioxolane;   (B14) degrading the 1,3-dioxolane obtained in step (B13) to form the second olefin in the form of its E-isomer.   
     
     
         22 . The method of  claim 21 , wherein the fourth olefin is an internal olefin. 
     
     
         23 . The method of  claim 22 , wherein the first and fourth olefin are identical. 
     
     
         24 . The method of  claim 22 , wherein the first and the fourth olefin are different from one another. 
     
     
         25 . The method of  claim 21 , wherein the fourth olefin is a terminal olefin. 
     
     
         26 . The method of  claim 25 , wherein the first and the fourth olefin are identical. 
     
     
         27 . The method of  claim 25 , wherein the first and the fourth olefin are different from one another. 
     
     
         28 . The method of  claim 21 , wherein the first and the fourth olefin are methyl 9-decenoate of formula 3, respectively, 
       
         
           
           
               
               
           
         
         and the second olefin is methyl E-9-octadecenedioate of formula 4 
       
       
         
           
           
               
               
           
         
       
     
     
         29 . The method of  claim 21 , wherein the metal complex is selected from a compound of formula (I): 
       
         
           
           
               
               
           
         
         wherein 
         M═Mo or W 
         X═O or N—R 5 ; 
         R 1 =H; 
         R 2 =CMe 3 ; CMe 2 Ph; or o-C1-6-alkoxyphenyl, optionally substituted; 
         R 3 =substituted aryloxy, preferably substituted phenyloxy, substituted naphthyl-2-oxy or substituted 5,6,7,8-tetrahydronaphthyl-2-oxy, or substituted naphthyl-1-oxy; 
         R 4 =pyrrol-1-yl, 2,5-dimethylpyrrol-1-yl; or 2,5-diphenylpyrrol-1-yl; or substituted or unsubstituted indol-1-yl; 
         R 5 =C 6-20  aryl or C 4-10  alkyl; optionally substituted. R z =neutral ligand; 
         n=0 or 1; 
         or 
         from a compound of formula (II): 
       
       
         
           
           
               
               
           
         
         wherein 
         M═Ru; 
         each of R 1  and L is a neutral ligand; 
         r=1-3; 
         each of R 4  and R 5  is independently bonded to M through sulfur or oxygen; or R 4  and 
         R 5  are halogen, preferably Cl; 
         R 14  is a carbene; 
         or 
         from a compound of formula (III): 
       
       
         
           
           
               
               
           
         
         wherein 
         Q is a hydrocarbylene, or alkyl-substituted hydrocarbylene; 
         Q* forms a carbon-ruthenium bond with the carbon from the R 3  group; 
         X 1  is nitrate, or C 1-20  alkylcarboxylate; 
         R 3  is cycloalkyl or an alkyl substituted cycloalkyl group; 
         R 4  is an alkyl substituted aryl group; 
         Z is alkyl; and 
         R 5 , R 6 , R 7  and R 8  are hydrogen. 
       
     
     
         30 . The method of  claim 29 , wherein the catalyst is selected from 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       (Mes=mesityl; Cy=cyclohexyl; DIPP=diisopropyphenyl; TBS=tert.-butyldimethylsilyl; mes=mesitylene; Ad=1-adamantyl; Ph=phenyl; TMS=trimethylsilyl, Me=methyl; Pr=propyl).