Functional n-heterocycles for solid-supported catalysis
AssigneeCalifornia Institute of Technology
InventorsRaymond Weitekamp, Robert H. Grubbs
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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.
Claims20
A compound of Formula (I):
- wherein:
- R1 and R2 are independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted cycloalkyl, carbonyl or sulfonyl;
- Q is selected from CR3R4, NR3, S, SO, or SO2;
- Y is selected from CR5R6, NR5, S, SO, or SO2, preferably selected such that Q and Y are not both NR3 and NR5;
- R3, R4, R5and R6 are independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, such that at least one of R3, R4, R5, and R6 comprises a functional group capable of attaching to a functional group on a solid support;
- and
- X− is a negatively charged counterion.
A compound of Formula (III):
- wherein:
- R1 and R2 are independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted cycloalkyl, carbonyl or sulfonyl;
- Q is selected from CR3R4, NR3, S, SO, or SO2;
- Y is selected from CR5R6, NR5, S, SO, or SO2, preferably selected such that Q and Y are not both NR3 and NR5;
- R3, R4, R5and R6 are independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, such that at least one of R3, R4, R5, and R6 comprises a functional group capable of attaching to a functional group on a solid support;
- and
- [M] is a transition metal complex.
The compound according to any one of the preceding claims, wherein R1 and R2 are independently substituted or unsubstituted aryl, e.g., mesityl.
The compound of according to any one of the preceding claims, wherein Q is CR3R4.
The compound according to any one of the preceding claims, wherein R3 and R4 are both H.
A method for preparing a compound of Formula (I):
- wherein:
- R1 and R2 are independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted cycloalkyl, carbonyl or sulfonyl;
- Q is selected from CR3R4, NR3, S, SO, or SO2;
- Y is selected from CR5R6, NR5, S, SO or SO2, preferably selected such that Q and Y are not both NR3 and NR5;
- R3, R4, R5and R6 are independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, such that at least one of R3, R4, R5, and R6 comprises a functional group capable of attaching to a functional group on a solid support;
- and
- X− is a negatively charged counterion;
- and
- the method comprises reacting the compound of Formula (VII) with a compound of Formula (VIII) in the presence of a base
- to provide the compound of Formula (I).
The compound according to any one of the preceding claims, wherein the phosphonate, phosphonic acid or semi-ester thereof, or a salt thereof, is tethered to a metal oxide support.
The compound according to any one of the preceding claims, wherein the phosphonate, phosphonic acid or semi-ester thereof, or a salt thereof, is tethered to alumina, silica, titania, zirconia or iron oxides.
The compound according to any one of the preceding claims, wherein R1, R2 or Z is a solubilizing group.
Dependencies are inferred from the claim text.