| US 7,544,819 B2 | ||
| Process for the asymmetric epoxidation of olefins | ||
| Wolfgang Maegerlein, Köln (Germany); Matthias Beller, Ostseebad Nienhagen (Germany); Christian Döbler, Lichtenhagen-Dorf (Germany); Man Kin Tse, Rostock (Germany); Santosh Bhor, Rostock (Germany); and Markus Klawonn, Rostock (Germany) | ||
| Assigned to Lanxess Deutschland GmbH, Leverkusen (Germany) | ||
| Filed on Feb. 04, 2005, as Appl. No. 11/51,279. | ||
| Claims priority of application No. 10 2004 005 725 (DE), filed on Feb. 05, 2004; and application No. 10 2004 024 709 (DE), filed on May 19, 2004. | ||
| Prior Publication US 2005/0203303 A1, Sep. 15, 2005 | ||
| Int. Cl. C07D 301/12 (2006.01); C07D 301/19 (2006.01) | ||
| U.S. Cl. 549—531 [549/529] | 6 Claims |
1. Process for preparing stereoisomerically enriched compounds of the formula (I),
 wherein
“*” is a carbon atom having an (R) or (S) configuration and R1, R2, R3 and R4 are each, independently of one another, hydrogen, alkyl, aryl, arylalkyl, haloalkyl or a radical of one of formulae (IIa)
to (IIf)
A-B-D-E (IIa)
A-E (IIb)
A-SO2-E (IIc)
A-B—SO2R6 (IId)
A-SO3W (IIe)
A-COW (IIf)
wherein, in the formulae (IIa) to (IIf)
A is absent or is an alkylene or haloalkylene radical and
B is absent or is oxygen or NR5, where
R5 is nitrogen, arylalkyl or aryl, and
D is a carbonyl group and
E is R6, OR6, NHR7 or N(R7)2,
where
R6 is alkyl, arylalkyl or aryl and
the radicals R7 each, independently of one another, alkyl, arylalkyl or aryl or the moiety N(R7)2 is a cyclic amino radical having from 4 to 12 carbon atoms and
W is OH, NH2, or OM, where M is an alkali metal ion, half an equivalent of an alkaline earth metal ion, an ammonium ion or an organic
ammonium ion,
or two of the radicals R1, R2, R3 and R4 are together part of a 3- to 7-membered ring having a total of from 3 to 16 carbon atoms,
comprising reacting compounds of the formula (III),
 where R1, R2, R3 and R4 are each, independently of one another, as defined above,
with compounds of the formula (IV),
R8—OOH (IV)
where R8 is hydrogen, alkyl or arylalkyl,
in the presence of a ruthenium complex which bears as ligands both compounds of the formula (V)
 where R9 is hydrogen, halogen, hydroxy, alkoxy, hydroxycarbonyl, alkoxycarbonyl, alkyl, arylalkyl or aryl and
L1 and L2 are each, independently of one another, a radical of the formula (VI-a) or a radical of the formula (VI-b)
 where “*1” and/or “*2” and/or “*3” are each an asymmetric carbon atom in the (R) or (S) configuration, the arrow points to
the point of bonding to the central pyridine ring and R10a, R10b and R11 are each, independently of one another, alkyl, alkoxyalkyl, trialkylsiloxyalkyl, alkoxycarbonyl, arylalkyl or aryl or R10a and R11 or R10a and R10b are part of a cyclic radical having a total of from 5 to 16 carbon atoms and R11 and/or R10a and/or R10b may also be hydrogen, and compounds of the formula (VII)
 where
X1, X2 and X3 are each, independently of one another, N, CH or CR12 and
R12 is hydrogen, halogen, hydroxy, hydroxycarbonyl, alkoxycarbonyl, alkoxy, alkoxyalkyl, arylalkyl or aryl and
n is 0, 1, 2 or 3, preferably 0 or 1 and particularly preferably 0,
and wherein the reaction is carried out in the presence of secondary or tertiary alcohols as solvents.
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