Process for the diastereoselective preparation of ruthenium complexes
View Patent ↗The present invention relates to a process for the preparation of a compound of formula (I), wherein X is —CH 2 —, —CH 2 —CH 2 —, —CH 2 —CH 2 —CH 2 — or —CH 2 —CH 2 —CH 2 —CH 2 —; Y 1 is —CH 2 —; —CH 2 —CH 2 — or —NH—; Y 2 is NHR 7 or SH; wherein R 7 is hydrogen, C 1 -C 4 alkyl or phenyl; R- 1 and R 2 , independently from each other, represent aliphatic or aromatic groups; R 3 and R 4 , independently from each other, represent aliphatic or aromatic groups; R 5 and R 6 are each hydrogen or represent together with the carbon atoms to which they are bonded, a phenyl ring; which process comprises reacting a compound of formula II [RuCI 2 (R 8 )n]m (II), wherein n is 1 and m is >1 which represents a polymeric structure if R 8 is a molecule containing two alkene or alkyne moieties coordinating in an hapto-2 coordination mode to the metal; or n is 4 and m is 1 if R 8 is a nitrogen, oxygen or sulfur containing molecule in which said nitrogen, oxygen or sulfur coordinate to the metal; in the presence of an inert solvent which boiling point is from 1 12° C. to 165° C. with a compound of formula (III), wherein R 5 , R 6 , Y 1 and Y 2 are as defined under formula I, and a phosphane of formula IV R 3 R 4 P—X—PR 1 R 2 (iv), wherein R 1 , R 2 , R 3 , R 4 and X are as defined under formula I.
1. A process for the preparation of a compound of formula I
wherein
X is —CH 2 —, —CH 2 —CH 2 —, —CH 2 —CH 2 —CH 2 — or —CH 2 —CH 2 —CH 2 —CH 2 —;
Y 1 is —CH 2 —; —CH 2 —CH 2 — or —NH—;
Y 2 is NHR 7 or SH; wherein R 7 is hydrogen, C 1 -C 4 alkyl or phenyl;
R 1 and R 2 , independently from each other, represent aliphatic or aromatic groups;
R 3 and R 4 , independently from each other, represent aliphatic or aromatic groups;
R 5 and R 6 are each hydrogen or together represent with the carbon atoms to which they are bonded, a phenyl ring; which process comprises reacting a compound of formula II
[RuCl 2 (R 8 )n]m (II),
wherein n is 1 and m is >1 which represents a polymeric structure if R 8 is a molecule containing two alkene or alkyne moieties coordinating in an hapto-2 coordination mode to the metal;
or n is 4 and m is 1 if R 8 is a nitrogen, oxygen or sulfur containing molecule in which said nitrogen, oxygen or sulfur coordinate to the metal;
in the presence of an inert solvent which boiling point is from 112° C. to 165° C. with a compound of formula III
wherein R 5 , R 6 , Y 1 and Y 2 are as defined under formula I, and a phosphane of formula IV
R 3 R 4 P—X—PR 1 R 2 (IV),
wherein R 1 , R 2 , R 3 , R 4 and X are as defined under formula I.
2. A process according to claim 1 for the preparation of a compound of formula I, wherein
X is —CH 2 —CH 2 —CH 2 —CH 2 —.
3. A process according to claim 2 for the preparation of a compound of formula I, wherein
R 8 is cyclooctadiene or bicyclo[2.2.1]hepta-2,5-diene if n is 1 and m >1; or is dimethylsulfoxide if n is 4 and m is 1.
4. A process according to claim 2 for the preparation of a compound of formula I, wherein
R 1 , R 2 , R 3 and R 4 are phenyl and
R 5 and R 6 are hydrogen or together represent with the carbon atoms to which they are bonded, a phenyl ring;
Y 1 is —CH 2 —, and
Y 2 is NH 2 .
5. A process according to claim 1 , wherein the compound of formula III is represented by compounds from the group consisting of the formulae
6. A process according to claim 1 performed as a one pot procedure.
7. A process according to claim 1 for the preparation of the compound of formula Ia
8. The compound of formula Ib