Chiral porous metal phosphonates for heterogeneous asymmetric catalysis

A chiral porous metal phosphonate according to Formula I:

• wherein M1 is a group IV metal, a lanthanide metal, or a first-row transition metal atom other than Ti, n=1-2 and is a quantity such that Formula I retains charge neutrality regardless of the M1 atom used;
• M2 is Ru, Rh, Ir, Os, Pt or Pd;
• X1 and X2 are covalently or ionically bonded to the M2 center, and each independently represents hydrogen, halogen, an alkoxy group or a carboxyl group;
• Ar1, Ar2, Ar3 and Ar4 independently represent a phenyl group substituted with from zero to five substituents selected from straight-chain or branched-chain lower alkyl groups, halogen, or lower alkoxy groups;
• L1 and L2 independently represent a coordinated solvent molecule, or donor atoms comprising half of a diamine moiety such that L1 and L2 are joined to give a chelating diamine, or a weakly coordinating ligand comprising an olefin;
• Y1 and Y2 independently represent a carbon or nitrogen atom;
• R1 and R2 independently represent hydrogen, a lower alkyl group, or a lower alkoxy group, or each pair of R1 and R2 can be the same or different and are bonded such that each R1 and R2 together with the attached ring form a ring selected from a substituted or unsubstituted tetrahydronaphthalene ring, a substituted or unsubstituted naphthalene ring, or a substituted or unsubstituted 1,3-benzodioxole ring, provided, however, that when Y1 is N, R1 is nothing;
• represents a bond independently linking the phosphonate groups to the benzene, pyridine, or pyrimidine ring or a ring formed by each of R1 and R2 as defined above, in any of the reasonable positions either directly or through one of the following linkages:
• an alkene group,
• an alkyl group,
• an aryl group or
• a styryl group;
• and
• each q is independently selected from 0 or 1.

A method for the stereoselective hydrogenation of a substrate capable of forming an asymmetric product by hydrogenation comprising contacting the substrate with a chiral porous metal phosphonate according to Formula I:

• wherein M1 is a group IV metal, a lanthanide metal, or a first-row transition metal atom other than Ti, n=1-2 and is a quantity such that Formula I retains charge neutrality regardless of the M1 atom used;
• M2 is Ru, Rh, Ir, Os, Pt or Pd;
• X1 and X2 are covalently or ionically bonded to the M2 center, and each independently represents hydrogen, halogen, an alkoxy group or a carboxyl group;
• Ar1, Ar2, Ar3 and Ar4 independently represent a phenyl group substituted with from zero to five substituents selected from straight-chain or branched-chain lower alkyl groups, halogen, or lower alkoxy groups;
• L1 and L2 independently represent a coordinated solvent molecule, or donor atoms comprising half of a diamine moiety such that L1 and L2 are joined to give a chelating diamine, or a weakly coordinating ligand comprising an olefin;
• Y1 and Y2 independently represent a carbon or nitrogen atom;
• R1 and R2 independently represent hydrogen, a lower alkyl group, or a lower alkoxy group, or each pair of R1 and R2 can be the same or different and are bonded such that each R1 and R2 together with the attached ring form a ring selected from a substituted or unsubstituted tetrahydronaphthalene ring, a substituted or unsubstituted naphthalene ring, or a substituted or unsubstituted 1,3-benzodioxole ring, provided, however, that when Y1 is N, R1 is nothing;
• represents a bond independently linking the phosohonate groups to the benzene, pyridine, or pyrimidine ring or a ring formed by each of R1 and R2 as defined above, in any of the reasonable positions either directly or through one of the following linkages:
• an alkene group,
• an alkyl group,
• an aryl group or
• a styryl group;
• and
• each q is independently selected from 0 or 1.

A compound according to one of the following formulas:

• wherein M2 is Ru, Rh, Ir, Os, Pt or Pd;
• X1 and X2 may be covalently or ionically bonded to the M2 center, and each independently represents hydrogen, halogen, an alkoxy group, or a carboxyl group;
• Ar1, Ar2, Ar3 and Ar4 independently represent a phenyl group substituted with from zero to five substituents selected from straight-chain or branched-chain lower alkyl groups, halogen, or lower alkoxy groups;
• L1 and L2 independently represent a coordinated solvent molecule, or donor atoms comprising half of a diamine moiety such that L1 and L2 are joined to give a chelating diamine;
• and
• each q is independently selected from 0 or 1.