Chiral diphenyldiphosphines and d-8 metal complexes thereof
OwnerBenoit Pugin, Ivo Steiner +2inventors
InventorsBenoit Pugin, Ivo Steiner, Rhony Niklaus Aufdenblatten, Antonio Togni
Life of this patent
Estimating the term…
Abstract
Compounds of formula III, 1 wherein R6 und R7 signify identical or different secondary phosphino; R8 is —CH2—OH, —CH2—NH2, —CH2—O—B—FU, —CH2—NH2—B—FU, or —O—B—FU; R9 has the same significance as R8 or is C1-C4-alkyl or C1-C4-alkoxy; or R8 and R9 together signify HOCH(CH2—O—)2, H2NCH—(CH2—O—)2, FU—B—OCH(CH2—O—)2 or FU—B—HNCH(CH2—O—)2; B is a bridging group; and FU is a functional group. The compounds may be bonded to inorganic or organic carriers. Their d-8 metal complexes are valuable catalysts for the enantioselective hydrogenation of prochiral organic compounds with carbon multiple bonds or carbon/hetero atom multiple bonds.
Claims10
Compounds of formula 1,
- 20
- wherein
- R1 is methyl chloride, methyl bromide or methyl iodide, R2 is C1-C4-alkyl or C1-C4-alkoxy or has the same significance as R1, and R3 is Br, I or —NH2.
Compounds of formula II,
- 21
- wherein
- R3 is Br, I or —NH2,
- R4 is hydroxymethyl, aminomethyl, hydroxy-, amino- or cyano-C2-C8-alkoxy, hydroxy-, amino- or cyano-C2-C8-alkoxymethyl, or hydroxy-, amino- or cyano-C2-C8-alkylaminomethyl, and R5 has the same significance as R4, or R5 is C1-C4-alkyl or C1-C4-alkoxy, or
- R4 and R5 together are HOCH(CH2—O—)2, H2NCH(CH2—O—)2, or hydroxy-, amino- or cyano-C2-C8-alkylOCH(CH2—O—)2.
Compounds of formula III,
- 22
- wherein
- R6 and R7 signify identical or different secondary phosphino,
- R8 is —CH2—OH, —CH2—NH2, —CH2—O—B—(FU)p, —CH2—NR′—B—(FU)p, or —O—B—(FU)p,
- R9 has the same significance as R8 or is C1-C4-alkyl or C1-C4-alkoxy, or
- R8 and R9 together signify HOCH(CH2—O—)2, H2NCH(CH2—O—)2, (FU)p—B—OCH(CH2—O—)2 or (FU)p—B—R′NCH(CH2—O—)2,
- R is H or C1-C4 alkyl;
- B is a bridging group,
- FU is a functional group,
- p is a number from 1 to 6, and
- NH2 groups are present as such or as masked isocyanate groups.
Metal complexes of formulae V, Va and Vb of d-8 metals with the compounds of formula III,
- 24
- whereby R6, R7, R8 and R9 have the above-mentioned significances and preferences;
- Y denotes two monoolefin ligands or one diene ligand;
- Me signifies a d-8 metal selected from the group Ir and Rh;
- D is —Cl, —Br or —I;
- and
- E is the anion of an oxyacid or complex acid;
- X2 and X2′ are identical or different and have the significance of D or E, or X2 and X2′ are allyl or 2-methylallyl, or X2 has the significance of D and E and X2′ is hydride.
Solid inorganic carrier, which has diphosphine ligands of formula IIIa that are bonded at the surface by one or two silyl groups of the radical of formula
- 25
- wherein the group B—FU in radicals R8 and R9 is a radical of formula
- —X3—C(O)—NH—R27—Si(R25)n(R26O)3-n
- wherein X3 signifies —O—, —NH— or NH(C1-C4-alkyl), R27 is C1-C12-alkylene, R26 is C1-C12 alkyl, R25 is C1-C4-alkyl or OR26 and n is 0, 1 or 2.
Dependencies are inferred from the claim text.