Use of immobilized molybdenum- and tungsten-containing catalysts in olefin cross metathesis

1. A method of forming an olefin from a first olefin and a second olefin in a metathesis reaction, comprising step (i):

(i) reacting the first olefin with the second olefin in the presence of a silica supported Mo-alkylidene or W-alkylidene catalyst, wherein the catalyst is of formula I

wherein

M is W or Mo;

R 1 is H, aryl, heteroaryl, alkyl, or heteroalkyl, optionally substituted, respectively;

R 2 and R 3 can be the same or different and are alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl, optionally substituted, respectively, or hydrogen;

R 5 is a residue R 6 —X—, wherein

R 6 is alkyl, aryl, heteroalkyl, heteroaryl, optionally substituted, respectively; (R 7 , R 8 , R 9 )Si; wherein R 7 , R 8 , R 9 are independently alkyl, alkoxy, phenyl or phenoxy, optionally substituted, respectively; (R 10 , R 11 , R 12 )C, wherein R 10 , R 11 , R 12 are independently phenyl, alkyl, optionally substituted, respectively;

X═O, S, or NR 13 , wherein R 13 is H; or alkyl or aryl, optionally substituted, respectively; or

R 5 is R 6 —CO—NR 13 , wherein R 6 and NR 13 have the meaning as defined above, or wherein R 6 and R 13 taken together form a carbon chain having from 2 to 6 carbon atoms; or

R 5 is an optionally substituted 4 to 8 membered N-containing ring, wherein N is linked to M; and

R 4 is a residue O—Si(O—) 3 , and represents silica to which M is linked forming a M-O—Si(O—) 3 moiety, and

wherein the first olefin and the second olefin are different from one another.

2. The method of claim 1 , wherein

(a) the first olefin is a cyclic olefin and the second olefin is a cyclic olefin; or

(b) the first olefin is a cyclic olefin and the second olefin is a non-cyclic olefin; or

(c) the first olefin is a non-cyclic olefin and the second olefin is a non-cyclic olefin.

3. The method of claim 1 , wherein the first olefin or the second olefin is a C 4 -C 30 olefin.

4. The method of claim 1 , wherein the first olefin has an internal olefinic double bond and the second olefin is ethylene.

5. The method of claim 1 , wherein

R 1 is aryl or adamant-1-yl, optionally substituted, respectively;

R 2 is —C(CH 3 ) 2 C 6 H 5 or —C(CH 3 ) 3 ;

R 3 is H;

R 5 is a residue R 6 —X—, wherein

X═O and R 6 is phenyl or phenyl substituted with up to five substituents independently selected from alkyl; alkoxy; phenoxy, phenyl, optionally substituted, respectively; or halogen; or

X═S and R 6 is phenyl or phenyl substituted with up to five substituents independently selected from alkyl; alkoxy; phenoxy, phenyl, optionally substituted, respectively; or halogen; or

X═O and R 6 is triphenylsilyl or triphenoxysilyl, optionally substituted, respectively; or tri(C 1 -C 4 alkyl)silyl or tri(C 1 -C 4 alkoxy)silyl;

X═O and R 6 is triphenylmethyl, optionally substituted; or

X═O and R 6 is 9-phenyl-fluorene-9-yl; or

X═O and R 6 is 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yl [(C 6 H 5 )(CF 3 ) 2 C]; or

X═O and R 6 is t-butyl, optionally substituted with one or more F groups.

6. The method of claim 1 , wherein

R 1 is phenyl or phenyl substituted with up to five substituents independently selected from C 1 -C 4 alkyl, C 1 -C 4 alkoxy, CF 3 , F, Cl, Br or phenyl or phenoxy, optionally substituted, respectively; and

X═O and R 6 is phenyl substituted with up to five substituents independently selected from C 1 -C 4 alkyl, C 1 -C 4 alkoxy, phenoxy, phenyl, halogen; or

X═S and R 6 is phenyl substituted with up to five substituents independently selected from C 1 -C 4 alkyl, C 1 -C 4 alkoxy, phenoxy, phenyl, halogen; or

X═O and R 6 is triphenylsilyl, triphenoxysilyl, tri(C 1 -C 4 alkyl)silyl or tri(C 1 -C 4 alkoxy)silyl; or

X═O and R 6 is t-butyl or (CF 3 )(CH 3 ) 2 C, (CF 3 ) 2 (CH 3 )C, (CF 3 ) 3 C or (C 6 H 5 )(CF 3 ) 2 C; or

R 5 is pyrrol-1-yl, 2,5-dimethylpyrrol-1-yl, or 2,5-diphenylpyrrol-1-yl.

7. The method of claim 1 , wherein R 1 is an electron donating group and R 5 is an electron withdrawing group.

8. The method of claim 7 , wherein

R 1 =phenyl substituted with up to five substituents independently selected from C 1 -C 4 alkyl, C 1 -C 4 alkoxy, phenyl, or phenoxy;

R 2 is —C(CH 3 ) 2 C 6 H 5 or —C(CH 3 ) 3 ;

R 3 is H;

R 5 is t-(CF 3 )(CH 3 ) 2 CO, t-(CF 3 ) 2 (CH 3 )CO, t-(CF 3 ) 3 CO, 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy, pyrrol-1-yl, 2,5-dimethylpyrrol-1-yl, or 2,5-diphenylpyrrol-1-yl.

9. The method of claim 1 , wherein R 1 is an electron withdrawing group and R 5 is an electron donating group.

10. The method of claim 1 , wherein

R 1 is phenyl substituted with up to five substituents independently selected from CF 3 , F, Cl, or Br;

R 2 is —C(CH 3 ) 2 C 6 H 5 or —C(CH 3 ) 3 ;

R 3 is H;

R 5 is t-(CH 3 ) 3 CO, tri(C 1 -C 4 )silyloxy, or tri(phenyl)silyloxy, phenoxy or phenylthio, wherein the phenyl moiety may be substituted with up to five substituents independently selected from C 1 -C 4 alkyl, C 1 -C 4 alkoxy, phenoxy, phenyl, or halogen.

11. The method of claim 1 , wherein both R 1 and R 5 are electron withdrawing groups.

12. The method of claim 1 , wherein

R 1 is phenyl substituted with up to five substituents independently selected from CF 3 , F, Cl, or Br;

R 2 is —C(CH 3 ) 2 C 6 H 5 or —C(CH 3 ) 3 ;

R 3 is H;

R 5 is (CF 3 )(CH 3 ) 2 CO, (CF 3 ) 2 (CH 3 )CO, (CF 3 ) 3 CO, (C 6 H 5 )(CF 3 ) 2 CO, pyrrol-1-yl, 2,5-dimethylpyrrol-1-yl, or 2,5-diphenylpyrrol-1-yl.

13. The method of claim 1 , wherein M is W.