Olefin metathesis catalysts and related methods

Patent metadata

Field	Value
Publication number	US-9242240-B2
Application number	US-201414479917-A
Country	US
Kind code	B2
Filing date	Sep 8, 2014
Priority date	Nov 22, 2006
Publication date	Jan 26, 2016
Grant date	Jan 26, 2016

Abstract

The present invention provides methods for the synthesis of catalysts and precursors thereof. Methods of the invention may comprise combining a catalyst precursor and at least one ligand to generate a catalytically active species, often under mild conditions and in high yields. In some cases, a wide variety of catalysts may be synthesized from a single catalyst precursor. Methods of the invention may also include the preparation of catalysts which, under reaction conditions known in the art, may have been difficult or impossible to prepare and/or isolate due to, for example, steric crowding at the metal center. The present invention also provides catalyst compositions, and precursors thereof, which may be useful in various chemical reactions including olefin metathesis. In some cases, methods of the invention may reduce the number of synthetic and purification steps required to produce catalysts and/or other reaction products, as well as reducing time, cost, and waste production.

First claim

What is claimed:

1. A method for synthesizing a catalyst, comprising:
providing a compound having the structure of formula I:

wherein:
M is Mo or W;
R 1 is alkyl, heteroalkyl, aryl, or heteroaryl, optionally substituted;
R 2 and R 3 can be the same or different and are hydrogen, alkyl, heteroalkyl, aryl, or heteroaryl, optionally substituted;
R 4 and R 5 can be the same or different and are heteroaryl, optionally substituted, or R 4 and R 5 are joined together to form a bidentate ligand with respect to M, optionally substituted; and wherein R 4 and R 5 each comprise at least one nitrogen atom; and
reacting the compound with an oxygen-containing ligand such that the oxygen-containing ligand replaces R 4 and R 5 to form a catalyst.

2. A method as in claim 1 , wherein R 4 and R 5 each coordinate M via a nitrogen atom.

3. A method as in claim 1 , wherein the oxygen-containing ligand is a bidentate ligand.

4. A method as in claim 1 , wherein the oxygen-containing ligand is a chiral ligand.

5. A method as in claim 1 , wherein the oxygen-containing ligand is attached to a surface via a covalent or a non-covalent bond.

6. A method as in claim 1 , wherein R 4 and R 5 are each pyrrolyl, optionally substituted, and coordinate M via the nitrogen atom of the pyrrolyl ring.

7. A method as in claim 1 , wherein R 1 is substituted phenyl.

8. A method as in claim 1 , wherein R 1 is adamantyl, optionally substituted.

9. A method as in claim 1 , wherein the oxygen-containing ligand is a hydroxy-substituted aryl group, wherein the hydroxyl group is deprotonated upon coordination to the metal center.

10. A method as in claim 1 , wherein the oxygen-containing ligand is monoalcohol, wherein the hydroxyl group is deprotonated upon coordination to the metal center.

11. A method as in claim 6 , wherein R 4 and R 5 are each pyrrolyl.

12. A method as in claim 7 , wherein R 1 is 2,6-dialkylphenyl.

13. A method as in claim 1 , further comprising,
catalyzing a reaction with the catalyst, wherein the catalyst is present at a concentration of less than 100 mM.

14. A method as in claim 13 , wherein the reaction is a carbon-carbon bond forming reaction.

15. A method as in claim 13 , wherein the reaction is an olefin metathesis reaction.

16. A method as in claim 13 , wherein the olefin metathesis reaction is a ring-closing reaction, a ring-opening reaction, or a cross-metathesis reaction.

17. A method as in claim 1 , wherein the catalyst has the structure:

wherein:
M is Mo or W;
R 1 is alkyl, heteroalkyl, aryl, or heteroaryl, optionally substituted;
R 2 and R 3 can be the same or different and are hydrogen, alkyl, heteroalkyl, aryl, or heteroaryl, optionally substituted;
R 6 and R 7 can be the same or different and are heteroalkyl or heteroaryl, optionally substituted, or R 6 and R 7 are joined together to form a bidentate ligand with respect to M, optionally substituted; and
wherein R 6 and R 7 each comprise at least one oxygen atom.

18. A method as in claim 17 , wherein M is Mo.

19. A method as in claim 17 , wherein R 6 and R 7 each coordinate M via an oxygen atom.

20. A method as in claim 17 , wherein R 6 and R 7 are joined together to form a biphenolate or binaptholate ligand.

21. A method as in claim 17 , wherein R 6 and R 7 are joined together to form a chiral ligand.

22. A method as in claim 1 , comprising
providing in a reaction vessel a compound having the structure:

wherein:
M is Mo or W;
R 1 is alkyl, heteroalkyl, aryl, or heteroaryl, optionally substituted;
R 2 and R 3 can be the same or different and are hydrogen, alkyl, heteroalkyl, aryl, or heteroaryl, optionally substituted;
R 4 and R 5 can be the same or different and are heteroaryl, optionally substituted, or R 4 and R 5 are joined together to form a bidentate ligand with respect to M, optionally substituted; and
wherein R 4 and R 5 each comprise at least one nitrogen atom; and
reacting in the reaction vessel the compound with an oxygen-containing ligand such that the oxygen-containing ligand replaces R 4 and R 5 to form a catalyst; and
catalyzing a reaction in the reaction vessel with the catalyst.

23. A method as in claim 22 , wherein the reaction is an olefin metathesis reaction.

24. A method as in claim 22 , wherein the catalyst has the structure:

wherein:
M is Mo or W;
R 1 is alkyl, heteroalkyl, aryl, or heteroaryl, optionally substituted;
R 2 and R 3 can be the same or different and are hydrogen, alkyl, heteroalkyl, aryl, or heteroaryl, optionally substituted;
R 6 and R 7 can be the same or different and are heteroalkyl or heteroaryl, optionally substituted, or R 6 and R 7 are joined together to form a bidentate ligand with respect to M, optionally substituted; and
wherein R 6 and R 7 each comprise at least one oxygen atom.

25. A method for synthesizing a metal complex, comprising:
providing a compound having the structure of formula I:

wherein:
M is Mo or W;
R 1 is alkyl, heteroalkyl, aryl, or heteroaryl, optionally substituted;
R 2 and R 3 can be the same or different and are hydrogen, alkyl, heteroalkyl, aryl, or heteroaryl, optionally substituted;
R 4 and R 5 can be the same or different and are heteroalkyl or heteroaryl, optionally substituted, or R 4 and R 5 are joined together to form a bidentate ligand with respect to M, optionally substituted; and wherein R 4 and R 5 each comprise at least one nitrogen atom; and
reacting the compound with an oxygen-containing ligand such that the oxygen-containing ligand replaces R 4 and R 5 ; wherein:
R 4 and R 5 each coordinate M via nitrogen;
the oxygen-containing ligand coordinates M via oxygen; and
the compound having the structure of formula I is other than:
Mo(NAr)(CHR')(NPh 2 ) 2 ,
Mo(NAr')(CHCMe 2 Ph)(NPh 2 ) 2 ,
Mo(NAr)(CHR')[N(t-Bu)( 3 , 5 -C 6 H 3 Me 2 )] 2 , and
Mo(NAr)(CHR')[N(i-Pr)( 3 , 5 -C 6 H 3 Me 2 )] 2 ,
wherein R' is t-Bu or CMe 2 Ph, Ar 2 , 6 -i-Pr 2 C 6 H 3 , and Ar'= 2 , 6 -Me 2 C 6 H 3 .

26. A method as in claim 25 , wherein R 1 is alkyl, heteroalkyl, aryl, or heteroaryl, optionally substituted.

27. A method as in claim 25 , wherein R 1 is not 2 , 6 -dialkylphenyl.

28. A method as in claim 25 , wherein R 4 and R 5 can be the same or different and are pyrrolyl, pyrazolyl, pyridinyl, pyrazinyl, pyrimidinyl, imidazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, indolyl, indazolyl, carbazolyl, optionally substituted.

29. A method for synthesizing a metal complex, comprising:
providing a compound having the structure of formula I:

wherein:
M is Mo or W;
R 1 is alkyl, heteroalkyl, aryl, or heteroaryl, optionall

Assignees

• Massachusetts Inst Technology

Inventors

• Hock Adam S
• Schrock Richard R

Classifications

• C07C2531/22

  Organic complexes · CPC title

• B01J2531/64

  Molybdenum · CPC title

• B01J31/122

  Metal aryl or alkyl compounds · CPC title

• B01J31/2291

  Olefins · CPC title

• B01J2531/66

  Tungsten · CPC title