Functional N-heterocycles for solid-supported catalysis

Patent metadata

Field	Value
Publication number	US-9573125-B2
Application number	US-201313928155-A
Country	US
Kind code	B2
Filing date	Jun 26, 2013
Priority date	Jun 26, 2012
Publication date	Feb 21, 2017
Grant date	Feb 21, 2017

Abstract

An efficient method for the preparation of backbone-substituted imidazolinium salts for use as N-heterocyclic carbene ligands, e.g., for organometallic catalysts is provided. These functionalized N-heterocyclic carbene ligands are used to prepare solid-supported catalysts, e.g., for olefin metathesis.

First claim

The invention claimed is:

1. A compound of Formula (II):

wherein:
R 1 and R 2 are independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl;
Q is CR 3 R 4 ;
X − is a negatively charged counterion;
R 3 and R 4 are independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl;
Z is selected from phosphate, phosphonate, and phosphonic acid, or a semi-ester thereof, or a salt thereof; and
n is an integer from 1-20.

2. The compound according to claim 1 , wherein R 1 and R 2 are independently substituted or unsubstituted aryl.

3. The compound according to claim 1 , wherein R 3 and R 4 are both H.

4. The compound according to claim 1 , having the structure of Formula (V):

wherein R 7 and R 8 are independently H or alkyl, or a salt thereof.

5. A method for preparing a transitional metal complex, comprising contacting a transition metal complex with an imidazolinium compound of claim 1 .

6. A method for preparing a solid-supported catalyst, comprising coupling a compound of claim 1 to a solid support bearing functional groups that react with Z.

7. The compound according to claim 1 , wherein Z is a phosphonate or a phosphonic acid or semi-ester thereof, or a salt thereof, and Z is tethered to a metal oxide support.

8. The compound according to claim 1 , wherein Z is a phosphonate or a phosphonic acid or semi-ester thereof, or a salt thereof, and Z is tethered to alumina, silica, titania, zirconia or iron oxides.

9. The compound according to claim 1 , wherein R 1 or R 2 is selected from substituted alkyl, substituted aryl, and substituted heteroaryl, wherein each substituent is a solubilizing group selected from a carboxylic acid, a sulfonic acid, a phosphoric acid, a phosphonic acid, a quaternary ammonium group, a heteroatom, and a heteroatomic group.

10. The compound according to claim 1 , wherein Z is a phosphonate.

11. A compound of Formula (IV):

wherein:
R 1 and R 2 are independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl;
Q is CR 3 R 4 ;
R 3 and R 4 are independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl;
Z is selected from phosphate, phosphonate, and phosphonic acid, or a semi-ester thereof, or a salt thereof;
n is an integer from 1-20; and
[M] is a transition metal complex.

12. The compound according to claim 11 , having the structure of Formula (VI):

wherein R 7 and R 8 are independently H or alkyl, or a salt thereof.

13. A method for preparing a compound of Formula (II)

wherein:
R 1 and R 2 are independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl;
Q is CR 3 R 4 ;
R 3 and R 4 are independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl;
Z is selected from phosphate, phosphonate, and phosphonic acid, or a semi-ester thereof, or a salt thereof;
n is an integer from 1-20; and
X − is a negatively charged counterion;
the method comprising reacting a compound of Formula (IX) with the compound of Formula (VIII) in the presence of a base

to provide the compound of Formula (II).

14. The method according to claim 13 , wherein R 1 and R 2 are independently substituted or unsubstituted aryl.

15. The method according to claim 13 , wherein R 3 and R 4 are both H.

16. The method according to claim 13 , wherein the compound has a structure of Formula (V):

wherein
R 7 and R 8 are independently H or alkyl, or a salt thereof; and
the method comprises reacting a compound of Formula (X) with a compound of Formula (XI) in the presence of a base

to provide the compound of Formula (V), wherein the identities of R 7 and R 8 may differ between the compound of Formula (X) and the compound of Formula (V).

Assignees

• California Inst Of Techn

Inventors

• Weitekamp Raymond
• Grubbs Robert H

Classifications

• B01J2231/543

  alkene metathesis · CPC title

• B01J2531/821

  Ruthenium · CPC title

• B01J2531/17

  Silver · CPC title

• B01J31/2273

  with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes · CPC title

• B01J2540/64

  Solubility enhancing groups · CPC title