Tetraphenylphenoxy tungsten oxo alkylidene complexes and methods of making same and use thereof

1. A compound of formula I:

wherein:

each of R 1 and R 2 is independently —R, —OR, —SR, —N(R) 2 , —OC(O)R, —S(O)R, —SO 2 R, —SO 2 N(R) 2 , —C(O)N(R) 2 , —NRC(O)R, or —NRSO 2 R; wherein each R is independently hydrogen or an optionally substituted group selected from C 1-10 aliphatic, C 1-10 heteroalkyl having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a 6-10 membered bicyclic saturated, partially unsaturated or aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 3-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur; or

two R groups are optionally taken together with the intervening atoms to form an optionally substituted 3-10 membered, monocyclic or bicyclic, saturated, partially unsaturated, or aryl ring having, in addition to the intervening atoms, 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur;

R 3 is optionally substituted 5-14 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, wherein at least one heteroatom is nitrogen; and wherein said heteroaryl ring is coordinated to W via said nitrogen atom;

R 4 is —OAr; wherein

Ar is 2,3,5,6-tetraphenylphenyl bearing in 4-position a substituent which is different from hydrogen; or

Ar is 2,3,5,6-tetraphenylphenyl bearing in 4-position a substituent which is different from hydrogen, and wherein one or more of the phenyl substituents in 2, 3, 5, or 6-position is/are substituted;

n is 0, 1 or 2; and

each R 5 is independently a phosphorus-containing ligand, wherein the phosphorus-containing ligand is bonded to W through a phosphorus atom,

wherein in Ar the substituent in 4-position is selected from —OR, —SR, —N(R) 2 , —OC(O)R, —S(O)R, —SO 2 R, —SO 2 N(R) 2 , —C(O)N(R) 2 , —NRC(O)R, or —NRSO 2 R; wherein each R is independently an optionally substituted group selected from C 1-10 aliphatic, C 1-10 heteroalkyl having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a 6-10 membered bicyclic saturated, partially unsaturated or aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 3-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur; or

two R groups are optionally taken together with the intervening atoms to form an optionally substituted 3-10 membered, monocyclic or bicyclic, saturated, partially unsaturated, or aryl ring having, in addition to the intervening atoms, 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur; or

wherein the substituent in 4-position is selected from halogen; nitro; cyano; —NH 2 ; or an ester group C(O)OR 7 , wherein R 7 is C 1-10 alkyl; or

each R 5 is a nitrogen-containing ligand, wherein the nitrogen-containing ligand is bonded to W through a nitrogen atom, and wherein the nitrogen-containing ligand is a pyridine; and

R 4 is —OAr; wherein

Ar is 2,3,5,6-tetraphenylphenyl; or

Ar is 2,3,5,6-tetraphenylphenyl, and wherein one or more of the phenyl substituents in 2, 3, 5, or 6-position is/are substituted; or

Ar is 2,3,5,6-tetraphenylphenyl bearing in 4-position a substituent which is different from hydrogen; or

Ar is 2,3,5,6-tetraphenylphenyl bearing in 4-position a substituent which is different from hydrogen, and wherein one or more of the phenyl substituents in 2, 3, 5, or 6-position is/are substituted;

and n is 0, 1 or 2,

wherein in Ar the substituent in 4-position is selected from —OR, —SR, —N(R) 2 , —OC(O)R, —S(O)R, —SO 2 R, —SO 2 N(R) 2 , —C(O)N(R) 2 , —NRC(O)R, or —NRSO 2 R; wherein each R is independently an optionally substituted group selected from C 1-10 aliphatic, C 1-10 heteroalkyl having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a 6-10 membered bicyclic saturated, partially unsaturated or aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 3-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur; or

two R groups are optionally taken together with the intervening atoms to form an optionally substituted 3-10 membered, monocyclic or bicyclic, saturated, partially unsaturated, or aryl ring having, in addition to the intervening atoms, 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur; or

wherein the substituent in 4-position is selected from halogen; nitro; cyano; —NH 2 ; or an ester group C(O)OR 7 , wherein R 7 is C 1-10 alkyl.

2. A compound of formula II:

wherein:

each of R 1 and R 2 is independently —R, —OR, —SR, —N(R) 2 , —OC(O)R, —S(O)R, —SO 2 R, —SO 2 N(R) 2 , —C(O)N(R) 2 , —NRC(O)R, or —NRSO 2 R; wherein each R is independently hydrogen or an optionally substituted group selected from C 1-10 aliphatic, C 1-10 heteroalkyl having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a 6-10 membered bicyclic saturated, partially unsaturated or aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 3-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur; or:

two R groups are optionally taken together with the intervening atoms to form an optionally substituted 3-10 membered, monocyclic or bicyclic, saturated, partially unsaturated, or aryl ring having, in addition to the intervening atoms, 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur;

R 3 is optionally substituted 5-14 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, wherein at least one heteroatom is nitrogen; and wherein said heteroaryl ring is coordinated to W via said nitrogen atom;

R 4 is —OAr; wherein

Ar is 2,3,5,6-tetraphenylphenyl; or

Ar is 2,3,5,6-tetraphenylphenyl, and wherein one or more of the phenyl substituents in 2, 3, 5, or 6-position is/are substituted;

n is 0, 1 or 2; and

each R 5 is independently a phosphorus-containing ligand, wherein the phosphorus-containing ligand is bonded to W through a phosphorus atom; and

wherein a compound of formula

is excluded.

3. The compound of claim 1 , wherein

one of R 1 and R 2 is hydrogen and the other is an optionally substituted group selected from C 1-10 aliphatic.

4. The compound of claim 1 , wherein

one of R 1 and R 2 is hydrogen and the other is selected from C(CH 3 ) 3 , C(CH 3 ) 2 C 6 H 5 , or phenyl or phenyl bearing in 2-position a residue —O—R 6 , wherein R 6 is selected from C 1-6 alkyl.

5. The compound of claim 1 , wherein

R 3 is selected from optionally substituted pyrrol-1-yl.

6. The compound of claim 1 , wherein

R 3 is selected from pyrrol-1-yl, 2,5-dimethylpyrrol-1-yl, 2,5-diphenylpyrrol-1-yl and indol-1-yl.

7. The compound of claim 1 , wherein

Ar is 2,3,5,6-tetraphenylphenyl bearing in 4-position a substituent selected from a substituent which is electron withdrawing or which is electron donating relative to a substituent which is hydrogen.

8. The compound of claim 1 , wherein Ar is 2,3,5,6-tetraphenylphenyl bearing in 4-position a substituent selected from methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, t-butyloxy; NH 2 , dimethylamino, diethylamino, di(n-propyl)amino, di(iso-propyl)amino; nitro; fluorine, chlorine, bromine or iodine; phenyl, optionally substituted; cyano; C(O)OCH 3 , C(O)OC 2 H 5 or C(O)OC 3 H 7 .

9. The compound of claim 1 , wherein Ar is 2,3,5,6-tetraphenylphenyl bearing in 4-position a substituent selected from Br, nitro, cyano, NH 2 , or N(CH 3 ) 2 .

10. The compound of claim 1 , wherein one or more of the phenyl substituents in 2, 3, 5, or 6 position is/are substituted with one or more substituents, and wherein said substituents are selected from —R, —OR, —SR, —N(R) 2 , —OC(O)R, —S(O)R, —SO 2 R, —SO 2 N(R) 2 , —C(O)N(R) 2 , —NRC(O)R, or —NRSO 2 R; wherein each R is independently an optionally substituted group selected from C 1-10 aliphatic, C 1-10 heteroalkyl having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a 6-10 membered bicyclic saturated, partially unsaturated or aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 3-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur; or:

two R groups are optionally taken together with the intervening atoms to form an optionally substituted 3-10 membered, monocyclic or bicyclic, saturated, partially unsaturated, or aryl ring having, in addition to the intervening atoms, 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur; or

a substituent selected from halogen; nitro; cyano or an ester group C(O)OR 6 , wherein R 6 is C 1-10 alkyl.

11. The compound of claim 1 , wherein

R 5 is selected from P(CH 3 ) 3 , P(CH 3 )(C 6 H 5 ) 2 , P(CH 3 ) 2 (C 6 H 5 ), or P(cyclohexyl) 3 ; or

R 5 is selected from pyridine or pyridine substituted with one or more substituents selected from C 1-6 alkyl, C 1-6 alkoxy, halogen, CN, or phenyl.

12. The compound of claim 1 , wherein the compound is selected from

wherein X is an electron-withdrawing substituent selected from Br, NO 2 , or CN; or

wherein X is an electron-donating substituent selected from NH 2 , or N(CH 3 ) 2 .

13. The compound of claim 2 , wherein the compound is

wherein X═H; or

wherein the compound is

14. A method of making the compound of formula I as defined in claim 1 , comprising

reacting a compound of formula (III)

wherein R 3 =R 4 =optionally substituted 5-14 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, wherein at least one heteroatom is nitrogen; and wherein said heteroaryl ring is coordinated to W via said nitrogen atom;

with 2,3,5,6-tetraphenylphenol or a substituted 2,3,5,6-tetraphenylphenol or the phenolate thereof, respectively;

wherein R 1 , R 2 , R 5 and n and the substituted 2,3,5,6-tetraphenylphenol have the meaning as defined in claim 1 .

15. The method of claim 14 , further comprising:

reacting a compound of formula (IV)

wherein R 1 , R 2 , R 5 and n have the meaning as defined in claim 14 ;

R 3 =R 4 =halogen;

with an optionally substituted salt of a 5-14 membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, wherein at least one heteroatom is a negatively charged nitrogen;

to afford the compound of formula (III).