Process for asymmetric epoxidation of olefins

摘要

Method for preparing steroisomerically enriched oxiranes (I) from the corresponding olefin and oxidizing agent. Method for preparing steroisomerically enriched oxiranes of formula (I) comprises reacting the corresponding olefin (III) with R 8OOH in presence of ruthenium complex (A) that includes, as ligands, both the pyridine derivative (V) and heterocyclic dicarboxylate (VII). R 1>-R 4>each : hydroxgen, (halo)alkyl, aryl, aralkyl, A-B-D-E, A-E, A-SO 2-E, A-B-SO 2R 6>, A-SO 3W or ACOW, or any two of them together form a 3-7 membered ring comprising a total of 3-16 C; A : (halo)alkylene or is absent; B : O or NR 5>, or is absent; R 5>hydrogen, aralkyl or aryl; D : CO; E = R 6>, OR 6>, NHR 7>or N(R 7>) 2; (MK#6) (MK#7) R 6>= alkyl, aralkyl or aryl; (MK#8) each R 7>= alkyl, aralkyl or aryl, or two R 7>complete a cyclic amino with 4-12 C; (MK#9) W = hydroxy, amino or OM; (MK#10) M = equivalent of alkali or alkaline earth metal or (organic) ammonium; (MK#11) R 8>= hydrogen, alkyl or aralkyl; (MK#12) R 9>= hydrogen, halo, hydroxy, alkoxy, carboxy, alkoxycarbonyl, alkyl, aralkyl or aryl; (MK#13) L 1>and L 2>= (VIa) and/or (VIb), including an asymmetric C atom (1-3) in (R) or (S) configuration; (MK#14) R 10a>, R 10b>and R 11>= hydrogen, alkyl, alkoxyalkyl, trialkylsiloxyalkyl, alkoxycarbonyl, aralkyl or aryl, or R 10a>with either of the others forms a ring of 5-16C; (MK#15) each of X 1>-X 3>= N, CH or CR 12>; (MK#16) R 12>= hydrogen, halo, hydroxy, carboxy, alkoxycarbonyl, alkoxy, alkoxyalkyl, aralkyl or aryl; (MK#17) n = 0-3, especially 0. Independent claims are also included for the following: (1) compounds (V) as new, where L 1>= L 2>= (VIa); R 10a>= hydrogen and R 11>= isopropyl or phenyl; and (2) ruthenium complexes that contain the new (V) of (1) and compound (VII). [Image].