Back to results
US 8,946,418 B1Granted
Chiral nitrogen-phosphorus ligands and their use for asymmetric hydrogenation of alkenes
AssigneeBoehringer Ingelheim International GmbH
InventorsNizar Haddad, Bo Qu, Jolaine Savoie, Chris Hugh Senanayake, Xudong Wei
Life of this patent
Estimating the term…
Abstract
The invention relates to a series of novel chiral nitrogen-phosphorus ligands of formulae (Ia) and (Ib): wherein R1-R3 and X are as defined herein. The invention also relates to chiral metal complexes prepared with these chiral nitrogen-phosphorus ligands. The chiral metal complexes are useful as catalysts for carrying out asymmetric hydrogenation.
Claims19
A compound of formula Ia, Ib, or a mixture thereof:
- wherein:
- X is O, S, or —NR5;
- R1 is —(C1-C6)alkyl, —CF3, —(C3-C10)carbocyclyl, -(5- to 11-membered)heterocarbocyclyl, —(C6-C14)aryl, -(5 to 11-membered)heteroaryl, or ferrocenyl;
- wherein said —(C3-C10)carbocyclyl, -(5- to 11-membered)heterocarbocyclyl, —(C6-C14)aryl and -(5 to 11-membered)heteroaryl of said R1 is optionally substituted with 1 to 3 substituents independently selected from —O(C1-C6)alkyl, —(C1-C6)alkyl, and —CF3;
- R2 is H, —O(C1-C6)alkyl, —(C1-C6)alkyl, —(C3-C10)carbocyclyl, -(5- to 11-membered)heterocarbocyclyl, —(C6-C14)aryl, -(5 to 11-membered)heteroaryl, —NR5R6, or —SR5;
- wherein said —(C3-C10)carbocyclyl, -(5- to 11-membered)heterocarbocyclyl, —(C6-C14)aryl, and -(5 to 11-membered)heteroaryl of said R2 is optionally substituted with 1 to 3 substituents independently selected from —O(C1-C6)alkyl, —(C1-C6)alkyl, and —CF3;
- R3 is —(C1-C6)alkyl substituted with 1 to 3 (5- to 6-membered)heteroaryl;
- wherein the (5- to 6-membered)heteroaryl ring is optionally substituted with 1 to 3 R4 substituents independently selected from —O(C1-C6)alkyl, —N—(C1-C6 alkyl)2, —(C1-C6)alkyl, phenyl, (5- to 11-membered)heteroaryl and —CF3;
- or
- R3 is selected from the group consisting of ortho-substituted pyridine, oxazoline, and chiral oxazoline, wherein each of said ortho-substituted pyridine, oxazoline, and chiral oxazoline is optionally substituted with 1 to 3 R4 substituents independently selected from —O(C1-C6)alkyl, —N—(C1-C6 alkyl)2, —(C1-C6)alkyl, phenyl, (5- to 11-membered)heteroaryl and —CF3;
- R5 and R6 are each independently H, —(C1-C6)alkyl, —CF3, —(C3-C10)carbocyclyl, -(5- to 11-membered)heterocarbocyclyl, —(C6-C10)aryl, or -(5 to 11-membered)heteroaryl;
- wherein each —(C1-C6)alkyl, —CF3, —(C3-C10)carbocyclyl, -(5- to 11-membered)heterocarbocyclyl, —(C6-C10)aryl, and -(5 to 11-membered)heteroaryl of said R5 and R6 is optionally independently substituted with 1 to 3 substituents independently selected from halo, —O(C1-C6)alkyl, —(C1-C6)alkyl, and —CF3.
9 more elements
A metal complex of formula (IIa), (IIb), or a mixture thereof:
- wherein
- M is a transition metal selected from Co, Ni, Pd, Pt, Cu, Ag, Au, Ru, Fe, Rh and Ir;
- A− is a counter anion;
- n is the oxidation state of the transition metal M;
- L1 and L2 are each olefins, or L1 and L2 together represent a diolefin;
- X is O, S, or —NR5;
- R1 is —(C1-C6)alkyl, —CF3, —(C3-C10)carbocyclyl, -(5- to 11-membered)heterocarbocyclyl, —(C6-C14)aryl, -(5 to 11-membered)heteroaryl, or ferrocenyl;
- wherein said —(C3-C10)carbocyclyl, -(5- to 11-membered)heterocarbocyclyl, —(C6-C14)aryl and -(5 to 11-membered)heteroaryl of said R1 is optionally substituted with 1 to 3 substituents independently selected from —O(C1-C6)alkyl, —(C1-C6)alkyl, and —CF3;
- R2 is H, —O(C1-C6)alkyl, —(C3-C10)carbocyclyl, -(5- to 11-membered)heterocarbocyclyl, —(C6-C14)aryl, -(5 to 11-membered)heteroaryl, —NR5R6, or —SR5;
- wherein said —(C3-C10)carbocyclyl, -(5- to 11-membered)heterocarbocyclyl, —(C6-C14)aryl, and -(5 to 11-membered)heteroaryl of said R2 is optionally substituted with 1 to 3 substituents independently selected from —O(C1-C6)alkyl, —(C1-C6)alkyl, and —CF3;
- R4 is selected from —O(C1-C6)alkyl, —(C1-C6)alkyl, phenyl and —CF3;
- R5 and R6 are each independently H, —CF3, —(C3-C10)carbocyclyl, -(5- to 11-membered)heterocarbocyclyl, (C6-C10)aryl, or -(5 to 11-membered)heteroaryl;
- wherein each —(C1-C6)alkyl, CF3, —(C3-C10)carbocyclyl, -(5- to 11-membered)heterocarbocyclyl, —(C6-C10)aryl, and -(5 to 11-membered)heteroaryl of said R5 and R6 is optionally independently substituted with 1 to 3 substituents independently selected from halo, —O(C1-C6)alkyl, —(C1-C6)alkyl, and —CF3.
10 more elements
Dependencies are inferred from the claim text.