Chiral nitrogen-phosphorus ligands and their use for asymmetric hydrogenation of alkenes

摘要

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.

主权项

1. 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.