TUNGSTEN IMIDO ALKYLIDENE O-BITET AND O-BINOL COMPLEXES AND USE THEREOF IN OLEFIN METATHESIS REACTIONS

1 . Compound of formula (I)

wherein

M=W;

R 1 is selected from phenyl substituted with one or more of halogen or CF 3 ;

R 2 is selected from pyrrol-1-yl or indol-1-yl, optionally substituted, respectively;

one of R 3 and R 4 is H, and the other is C(CH 3 ) 2 C 6 H 5 ;

LO— is

wherein X 1 and X 2 are independently selected from halogen, CF 3 and C 6 F 6 ; or

X 1 =X 2 =halogen, CF 3 or C 6 F 5 ;

P is C 1 -C 6 alkyl, or a silyl group; and

N is a neutral ligand bound to M,

wherein n is 1 or 2, when LO— is a O-bitet ligand, or

wherein n is 0, 1, or 2, when LO— is a O-binol ligand.

2 . Compound of formula (II)

wherein

M=W;

R 1 is selected from aryl, alkyl and cycloalkyl, each of which is optionally substituted;

R 2 is selected from pyrrol-1-yl or indol-1-yl, optionally substituted, respectively;

one of R 3 and R 4 is H, and the other is C(CH 3 ) 2 C 6 H 5 ; wherein the phenyl group of the C(CH 3 ) 2 C 6 H 5 moiety is additionally substituted in o-position with a group selected from O—(C 1 -C 6 alkyl) and —CH 2 —O—(C 1 -C 6 alkyl);

LO— is

wherein X 1 and X 2 are independently selected from halogen, CF 3 and C 6 F 6 ; or

X 1 =X 2 =halogen, CF 3 or C 6 F 5 ;

P is C 1 -C 6 alkyl, or a silyl group; and

N is a neutral ligand bound to M, wherein n is 0, 1 or 2.

3 . Compound of formula (III)

wherein

M is W;

R 1 is selected from aryl, alkyl and cycloalkyl, each of which is optionally substituted;

R 2 is pyrrol-1-yl or indol-1-yl, optionally substituted, respectively;

R 3 is H;

R 4 is selected from O—(C 1 -C 6 alkyl), and —CH 2 —O—(C 1 -C 6 alkyl);

R 5 is/are one or more independently selected from H, C 1 -C 6 alkyl, O—(C 1 -C 6 alkyl), phenyl, halogen, NO 2 , CN, and NHC(O)—(C 1 -C 6 alkyl);

LO— is

wherein

X 1 and X 2 are independently selected from halogen, CF 3 and C 5 F 5 ; or

X 1 =X 2 =halogen, CF 3 or C 6 F 5 ;

P is C 1 -C 6 alkyl, or a silyl group; and

N is a neutral ligand bound to M, wherein n is 0, 1 or 2.

under the proviso that a compound of formula

is excluded.

4 . Compound of formula (V)

wherein

M is W;

R 1 is selected from aryl, alkyl and cycloalkyl, each of which is optionally substituted;

R 2 is pyrrol-1-yl or indol-1-yl, optionally substituted, respectively;

R 3 is

wherein * denotes the bond between R 3 and the alkylidene carbon;

R 4 is selected from O—(C 1 -C 6 alkyl), and —CH 2 —O—(C 1 -C 6 alkyl);

R 5 is/are one or more independently selected from H, C 1 -C 6 alkyl, O—(C 1 -C 6 alkyl), phenyl, halogen, NO 2 , CN, and NHC(O)—(C 1 -C 6 alkyl);

LO— is

wherein

X 1 and X 2 are independently selected from halogen, CF 3 and C 6 F 5 ; or

X 1 =X 2 =halogen, CF 3 or C 6 F 5 ;

P is C 1 -C 6 alkyl, or a silyl group; and

N is a neutral ligand bound to M, wherein n is 0, 1 or 2.

5 . Compound of formula (VI)

wherein

M is W;

Ar is selected from phenyl, naphthyl and anthracenyl, optionally substituted, respectively;

R 1 is selected from aryl, alkyl and cycloalkyl, each of which is optionally substituted;

R 2 is pyrrol-1-yl or indol-1-yl, optionally substituted, respectively;

R 3 is selected from H;

LO— is

wherein

X 1 and X 2 are independently selected from halogen, CF 3 and C 6 F 5 ; or

X 1 =X 2 =halogen, CF 3 or C 8 F 5 ;

P is C 1 -C 6 alkyl, or a silyl group; and

N is a neutral ligand bound to M, wherein n is 0, 1 or 2;

preferably wherein, when the compound of formula (VI) is a compound of formula (VI-A),

R 4 is R 5 ; and

R 5 is/are one or more independently selected from H, C 1 -C 6 alkyl, O—(C 1 -C 6 alkyl), phenyl, halogen, NO 2 , CN, and NHC(O)—(C 1 -C 6 alkyl); wherein O—(C 1 -C 6 alkyl) is not in o-position.

6 . Compound of any one of claims 2 to 5 , wherein R 1 is selected from the group consisting of phenyl substituted with one or more of C 1 -C 6 alkyl, O—(C 1 -C 6 alkyl), phenyl, halogen and CF 3 ; t-butyl, and 1-adamantyl.

7 . Compound of any one of the preceding claims, wherein R 1 is selected from 2,6-dichlorophenyl, pentafluorophenyl and o-trifluoromethylphenyl.

8 . Compound of any one of the preceding claims, wherein R 2 is selected from pyrrol-1-yl, 2,5-dimethyl-pyrrol-1-yl, 2,5diethyl-pyrrol-1-yl, 2,5-diphenyl-pyrrol-1-yl, and indol-1-yl.

9 . Compound of any one of the preceding claims, wherein

LO— has (R) configuration; or

LO— has (S) configuration; or

LO is racemic.

10 . Compound of claim 3 ,

wherein

M=W, R 1 =2,6-dichlorophenyl; R 2 =2,5-dimethyl-pyrrol-1-yl; R 3 =H; R 4 =OCH 3 ; R 5 =H; X 1 =X 2 =F;

M=W, R 1 =2,6-dichlorophenyl; R 2 =2,5-dimethyl-pyrrol-1-yl; R 3 =H; R 4 =OCH 3 ; R 5 =H; X 1 =X 2 =Cl;

M=W, R 1 =2,6-dichlorophenyl; R 2 =2,5-dimethyl-pyrrol-1-yl; R 3 =H; R 4 =OCH 3 ; R 5 =R 6 =H; X 1 =X 2 =l;

M=W, R 1 =2,6-dichlorophenyl; R 2 =2,5-dimethyl-pyrrol-1-yl; R 3 =H; R 4 =OCH 3 ; R 5 =H; X 1 =X 2 =CF 3 ;

M=W, R 1 =2,6-dichlorophenyl; R 2 =2,5-dimethyl-pyrrol-1-yl; R 3 =H; R 4 =OCH 3 ; R 5 =H; X 1 =X 2 =C 6 F 5 .

11 . Compound selected from one of the following compounds (TBS=t-butyldimethylsilyl):

12 . Method of performing a metathesis reaction, wherein the metathesis reaction is selected from ethenolysis of an internal olefin, cross-metathesis of an olefin, and a ring-closing metathesis reaction, the method comprising:

performing the metathesis reaction in the presence of a compound of formula (I), (II), (III), (IV) or (VI) as defined in any one of claims 1 to 10 including the disclaimed compound in claim 3 .

13 . Method of claim 12 , wherein ethenolysis is ethenolysis of an unsaturated fatty acid ester, and the cross-metathesis is homo-metathesis of an unsaturated fatty acid ester.

14 . Method of performing a metathesis reaction, wherein the metathesis reaction is ethenolysis of an unsaturated fatty acid ester, or the metathesis reaction is homo-metathesis of an unsaturated fatty acid ester, or a ring-dosing reaction, the method comprising:

performing the metathesis reaction in the presence of a compound of formula (V)

wherein

M=W;

R 1 is phenyl substituted with one or more of halogen or CF 3 ;

R 2 is pyrrol-1-yl or indol-1-yl, optionally substituted;

one of R 3 and R 4 is H, and the other is C(CH 3 ) 2 C 6 H 5 ;

LO— is

wherein X 1 and X 2 are independently selected from halogen, CF 3 and C 6 F 6 ; or

X 1 =X 2 =halogen, CF 3 or C 6 F 5 ;

P is C 1 -C 6 alkyl, or a silyl group; and

N is a neutral ligand bound to M, wherein n is 0, 1 or 2.

15 . Method of any one of claims 13 to 14 , wherein said unsaturated fatty acid ester is a natural oil.

16 . Method of any one of claims 13 to 15 , wherein said unsaturated fatty acid ester is a methyl ester (FAME).

17 . Method of claim 16 , wherein the methyl ester (FAME) is methyl oleate or methyl linolate or methyl linolenoate or a mixture of two or three thereof.

18 . Method of any one of claims 12 to 17 , wherein said olefin to be metathesized is purified prior to metathesis by subjecting same to a trialkyl aluminium compound.

19 . Compound of formula (I), (II), (III), (IV), or (VI) as defined in any one of claims 1 to 10 , wherein LO— is racemic, or

method of claim 12 or 13 , wherein in the compound of formula (I), (II), (III), (IV), or (VI) LO— is racemic; or

method of any one of claims 14 to 18 , wherein in the compound of formula (V) LO— is racemic.

20 . Composition comprising a compound of formula (I), (II), (III), (IV), (V) or (VI) and an olefin to be metathesized, wherein the olefin to be metathesized has been subjected to a trialkyl aluminium compound prior to metathesis.

21 . Composition of claim 20 , wherein in the compound of formula (I), (II), (III), (IV), (V) or (VI) LO— is racemic.

22 . Compound of formula (I), (II), (III), (IV), or (VI) as defined in any one of claims 1 to 10 wherein the neutral ligand N is selected from a nitrile, a phosphine, or a pyridine; or

method of any one of claims 12 to 13 , wherein in the compound of formula (I), (II), (III), (IV), or (VI) the neutral ligand N is selected from a nitrile, a phosphine, or a pyridine; or

method of any one of claims 14 to 18 , wherein in the compound of formula (V) the neutral ligand N is selected from a nitrile, a phosphine, or a pyridine; or

composition of claim 20 or 21 , wherein in the compound of formula (I), (II), (III), (IV), (V) or (VI) the neutral ligand N is selected from a nitrile, a phosphine, or a pyridine.

23 . Compound, method or composition of claim 22 , wherein the pyridine is 2,2′-dipyridine or 1,10-phenanthroline, and wherein n=1.

24 . Compound, method or composition of claim 23 , wherein the compound of formula (III) is

25 . Compound 4, wherein the aryloxy-ligand is in racemic form.