Patent ID: 6020527
Filing Date: 2000-02-01
Classification: C07B,C07C

Abstract:
Process for the stereospecific isomerisation of prochiral allylic systems represented by the formula ##STR24## in which R.sup.1 .noteq.R.sup.2, each being selected from the group consisting of alkyl and alkenyl groups containing from 1 to 12 carbon atoms, aryl groups, optionally substituted by a hydroxy group, R.sup.3 and R.sup.4 are, independently from each other, selected from the group consisting of hydrogen, alkyl and alkenyl groups from C.sub.1 to C.sub.12 and aryl groups, R.sup.5 is selected from the group consisting of hydrogen and alkyl and cycloalkyl groups containing from 1 to 8 carbon atoms, R.sup.6 is selected from the group consisting of alkyl and cycloalkyl groups containing from 1 to 8 carbon atoms, or R.sup.5 and R.sup.6 are taken together with the nitrogen atom to form a ring selected from the group consisting of 5-membered rings, 6-membered rings and 6-membered rings which further contain an oxygen atom, into the group of compounds consisting of enamines as represented by the formula ##STR25## in which the symbols R.sup.1 -R.sup.6 are as defined above, and imines as represented by the formula ##STR26## in which the symbols R.sup.1 -R.sup.4 and R.sup.6 are as defined above and R.sup.5 is hydrogen, by means of catalysts selected from the group consisting of Rh, Ir and Ru compounds carrying at least one chiral phosphorous ligand, wherein said ligand is a compound represented by the formula (V) ##STR27## in which the carbon atom marked by an asterisk is an asymmetric carbon atom, X is hydrogen or a bridging group bonded to a polymer and represented by formula (A).sub.n --B--P in which n is 0 or 1,A is an appropriate spacer group containing at least one atom of oxygen, sulfur, silicon, nitrogen or carbon,B is a linking group between the cyclopentadienyl rest and the polymer P when n=0, or between A and P when n=1, andP is an organic or inorganic polymer,A. Z stands for a phosphorous atom; R.sub.1 is selected from the group consisting of alkyl groups from C.sub.1 to C.sub.8, phenyl groups, optionally substituted by 1 to 3 alkyl or alkoxy groups from C.sub.1 to C.sub.4 ; R.sub.2, R.sub.3, R.sub.10 and R.sub.11 are, independently from each other, selected from the group consisting of alkyl groups from C.sub.1 to C.sub.12, cycloalkyl groups from C.sub.5 to C.sub.12, optionally substituted by an alkyl or alkoxy group from C.sub.1 to C.sub.4, and phenyl groups optionally carrying from 1 to 3 substituents selected from the group consisting of alkyl and alkoxy groups from C.sub.1 to C.sub.4, --SiR.sub.4 R.sub.5 R.sub.6, halides, --SO.sub.3 M, --CO.sub.2 M, --PO.sub.3 M, --NR.sub.7 R.sub.8 and --[.sup.+ NR.sub.7 R.sub.8 R.sub.9 ]Y.sup.- ; or R.sub.2, R.sub.3, R.sub.10 and R.sub.11 represent, independently from each other, a group of formula ##STR28## in which R.sub.12 is an alkyl group from C.sub.1 to C.sub.5, partially or totally fluorinated; R.sub.13 is selected from the group consisting of alkyl and alkoxy groups from C.sub.1 to C.sub.4, --SiR.sub.4 R.sub.5 R.sub.6, halide, --SO.sub.3 M, --CO.sub.2 M, --PO.sub.3 M, --NR.sub.7 R.sub.8 and --[NR.sub.7 R.sub.8 R.sub.9 ]Y.sup.- ;m is an integer from 1 to 3; n is 0 or an integer from 1 to 4, the sum of m+n being from 1 to 5;R.sub.4, R.sub.5 and R.sub.6 are, independently from each other, selected from the group consisting of alkyl groups from C.sub.1 to C.sub.12 and phenyl groups; R.sub.7 and R.sub.8, taken separately, are each selected from the group consisting of hydrogen, alkyl groups from C.sub.1 to C.sub.12 and phenyl groups, or, taken together, represent a group selected from the group consisting of tetramethylene, pentamethylene and 3-oxa-1,5-pentylene; and R.sub.9 is hydrogen or an alkyl group from C.sub.1 to C.sub.4 ;M is hydrogen or an alkali metal; and Y is the anion of a monobasic acid;orB. Z is nitrogen, R.sub.1 is selected from the group consisting of alkyl groups from C.sub.1 to C.sub.8 and phenyl groups, optionally substituted by 1 to 3 substitutents selected from the group consisting of alkyl and alkoxy groups from C.sub.1 to C.sub.4, R.sub.2 and R.sub.3 are, independently from each other, selected from the group consisting of alkyl groups from C.sub.1 to C.sub.12, cycloalkyl groups from C.sub.5 to C.sub.12 and phenyl groups optionally substituted by 1 to 3 alkyl groups from C.sub.1 to C.sub.4 ; or R.sub.2 and R.sub.3 are taken together with the nitrogen to form a 5 to 12-membered ring, optionally comprising further nitrogen or oxygen atoms; and R.sub.10 and R.sub.11 are each a phenyl group; or said ligand is represented by the general formula ##STR29## in which R.sub.1 is selected from the group consisting of hydrogen, fluoride, alkyl groups, acyl groups, and a group of formula XR.sub.5 in which X is oxygen or sulfur and R.sub.5 is selected from the group consisting of hydrogen, alkyl groups and aryl groups;R.sub.2 is selected from the group consisting of hydrogen and alkyl groups, with the stereochemistry of the C-.sub.13, C-.sub.14 and C-.sub.17 being .alpha. or .beta.;R.sub.3 is selected from the group consisting of hydrogen, fluoride, alkyl groups, aryl groups, trialkylsilyl groups and a group of formula XR.sub.6 in which X has the sense indicated above and R.sub.6 is selected from the group consisting of hydrogen, alkyl groups, aryl groups and trifluoromethylsulfonyl groups;R.sub.4 is a substituent in position 6 or 7 of the steroide and is selected from the group consisting of hydrogen, fluoride, alkyl groups, aryl groups and a group of formula YR.sub.7 in which Y is oxygen, sulfur or a trialkylsilyl group and R.sub.7 is selected from the group consisting of hydrogen, alkyl groups, aryl groups and a trifluoromethylsulfonyl group; the B cycle of the steroide being saturated or carrying two double bonds.