Molecular weight-enlarged ligands for asymmetric, homogeneously soluble hydrogenation catalysts, process for the production thereof and use

A process for the production of a ligand, comprising a step selected from the group consisting of(a)-(c):

• (a) binding a homochiral active center to a monomer directly or through a polymer linker to provide a modified monomer, and polymerizing said modified monomer in the presence of one or more unmodified monomers;
• (b) binding a homochiral active center to a polymer, either directly or through a polymer linker;
• and
• (c) carrying out either of steps (a) or (c) and further polymerizing the resulting polymer with one or more additional polymers, wherein said one or more additional polymers optionally comprise one or more homochiral active centers;
• wherein said one or more homochiral active centers are selected from the group consisting of compounds having the formulas in the following table, and combinations thereof:
• n = 0-5 n = 0-5 R = cyclohexyl or (C6-C18) aryl R′ = H, polymer linker or molecular weight enlarging polymer X = PR2or OMe R = cyclohexyl or (C6-C18) aryl R′ = CH3, OMe, CF3, H, tert.Bu R = H, CF3, OMe, CH3 R = H, (C1-C8) alkyl, polymer linker or molecular weight enlarging polymer R = H, (C1-C8) alkyl, polymer linker or molecular weight enlarging polymer R = cyclohexyl or (C6-C18) aryl R = cyclohexyl or (C6-C18) aryl R′ = (C1-C8) alkyl, (C7-C19) aralkyl, (C6-C18) aryl, polymer linker or molecular weight enlarging polymer R″ = (C1-C8) alkyl, polymer linker or molecular weight enlarging polymer R = H, polymer linker or molecular weight enlarging polymer R′ = (C1-C8) alkyl, (C7-C19) aralkyl or (C6-C18) aryl R = cyclohexyl or (C6-C18) aryl R′ = (C1-C8) alkyl, H, polymer linker or molecular weight enlrging polymer R″ = H, polymer linker or molecular weight enlarging polymer X = NR′2, NR′H, OMe or OAc Y = PR2 or H R = cyclohexyl or (C6-C18) aryl R′ = (C1-C8) alkyl, (C6-C18) aryl orH R″ = polymer linker or molecular weight enlarging polymer n = 0, 1 or 2 R = H, (C1-C8) alkyl, polymer linker or molecular weight enlarging polymer R = cyclohexyl or (C6-C18) aryl R′ = H, (C1-C8) alkyl or (C6-C18) aryl R = (C1-C8) alkyl R′ = H, O-(C1-C8) alkyl, O-(C7-C19) aralkyl, O-(C6C18aryl or OH R = cyclohexyl or (C6-C18) aryl R′ = H, polymer linker or molecular weight enlarging polymer R = cyclohexyl or (C6-C18) aryl R′ = H, polymer linker or molecular weight enlarging polymer R = H, (C1-C8) alkyl, (C7-C19) aralkyl, polymer linker or molecular weight enlarging polymer R = cyclohexyl or (C6-C18) aryl R′ = H, (C1-C8) alkyl, polymer linker or molecular weight enlarging polymer R″= H, (C1-C8) alkyl, (C7-C19) aralkyl, (C6-C18) aryl, polymer linker or molecular weight enlarging polymer R = cyclohexyl or (C6-C18) aryl R′ = H, (C1-C8) alkyl, (C7-C19) aralkyl, (C6-C18) aryl, polymer linker or molecular weight enlarging polymer R = cyclohexyl or (C6-C18) aryl X = CH2, O, S, PR or NH R = H, polymer linker or molecular weight enlarging polymer R = H, polymer linker or molecular weight enlarging polymer (n = 1-6) R = (C1-C8) aryl, (C7-C19) aralkyl, (C6-C18) aryl, polymer linker or molecular weight enlarging polymer R = cyclohexyl or (C6-C18) aryl R′ = H, (C1-C8) alkyl, (C7-C19) aralkyl, (C6-C18) aryl, polymer linker or molecular weight enlarging polymer n = 0-5 n = 0,1 R = (C1-C8) alkyl, H R′ = H, (C1-C8) alkyl, (C7-C19) aralkyl, (C6-C18) aryl, polymer linker or molecular weight enlarging polymer R = (C1-C8) alkyl or (C6-C18) aryl, n = 0-5 R = (C1-C8) alkyl or (C7-C19) aralkyl, (C6-C18) aryl R = cyclohexyl or (C6-C18) aryl R′ = (C1-C8) alkyl, (C6-C18) aryl, polymer linker or molecular weight enlarging polymer R″ = H, (C1-C8) alkyl, (C7-C19) aralkyl, (C6-C18) aryl, polymer linker or molecular weight enlarging polymer OR′, OAc, NR′2 or NH2 R = cyclohexyl or(C6-C18) aryl R′ = (C1-C8) alkyl, (C6-C18) aryl, polymer linker or molecular weight enlarging polymer R″ = H, (C1-C8) alkyl, (C6-C18) aryl, OR′, OAc, NR′2, NH2, polymer linker or molecular weight enlarging polymer R = O, S, NH R′ = H, (C1-C8) alkyl, (C7-C19) aralkyl, (C6-C18) aryl, polymer linker or molecular weight enlarging polymer R″ = (C1-C8) alkyl, (C7-C19) aralkyl or (C6-C18) aryl R = (C1-C8) alkyl, (C7-C19) aralkyl or (C6-C18) aryl R = (C1-C8) alkyl, (C7-C19) aralkyl or (C6-C18) aryl R′ = (C1-C8) alkyl, (C7-C19) aralkyl or (C6-C18) aryl R = polymer linker or molecular weight enlarging polymer or H R′ = (C1-C8) alkyl, (C7-C19) aralkyl, (C6-C18) aryl, polymer linker or molecular weight enlarging polymer Bis(e,4-diarylphosphinyl)pyrrolidine
• wherein a line extending from said formulas of said one or more homochiral active centers represents a bond of a binding site both for the polymer or for the polymer linker;
• wherein said polymer linker is a member selected from the group consisting of formulae a)-g):
• a) —Si(R2)— b) —(SiR2—O)n— n = 1-10000;
• c) —(CHR—CHR—O)n— n = 1-10000;
• d) —(X)n— n = 1-20;
• e) Z—(X)n— n = 0-20;
• f) —(X)n—W n = 0-20;
• and g) Z—(X)n—W n = 0-20;
• wherein
• R is H, (C1-C8) alkyl, (C6-C18) aryl, (C7-C19) aralkyl, or ((C1-C8) alkyl)1-3-(C6-C18) aryl;
• X is (C6-C18) arylene, (C1-C8) alkylene, (C1-C8) alkenylene, ((C1-C8) alkyl1-3-(C6-C18) arylene, or (C7-C19) aralkylene;
• Z is C(═O)O—, C(═O)NH—, C(═O)—, NR, O, CHR, CH2, C═S, S, PR, Z being bound directly to said polymer;
• and
• W is C(═O)O—, C(═O)NH—, C(═O)—, NR, O, CHR, CR2, C═S, S, PR, W being bound directly to said homochiral active center;
• wherein the polymer is a member selected from the group consisting of polyacrylates, polyvinylpyrrolidinones, polysiloxanes, polybutadienes, polyisoprenes, polyalkanes, polystyrenes, polyoxazolines and mixtures thereof.

A process comprising producing one or more enantiomerically enriched organic compounds, comprising:

• performing a reaction on a starting material comprising at least one non-chiral site to convert said non-chiral site into a chiral site;
• wherein said reaction is performed in the presence of a catalyst for said reaction, said catalyst comprising at least one molecular weight-enlarged ligand, which comprises:
• a molecular weight-enlarging polymer;
• optionally, a polymer linker;
• and
• at least one homochiral active center;
• wherein said active center is bound to said molecular weight-enlarging polymer through said polymer linker or is bound directly to said molecular weight-enlarging polymer;
• and
• wherein said active center is selected from the group consisting of compounds having the formulas in the following table, and combinations thereof:
• n = 0-5 n = 0-5 R = cyclohexyl or (C6-C18) aryl R′ = H, polymer linker or molecular weight enlarging polymer X = PR2 or OMe R = cyclohexyl or (C6-C18) aryl R′ = CH3, OMe, CF3, H or tert.Bu R = H, CF3, OMe or CH3 R = H, (C1-C8) alkyl or polymer linker or molecular weight enlarging polymer R = H, (C1-C8) alkyl or polymer linker or molecular weight enlarging polymer R = cyclohexyl or (C6-C18) aryl R = cyclohexyl, (C6-C18) aryl R′= (C1-C8) alkyl, (C7-C19) aralkyl, (C6-C18) aryl, polymer linker or molecular weight enlarging polymer R″ = (C1-C8) alkyl, polymer linker or molecular weight enlarging polymer R = H, polymer linker or molecular weight enlarging polymer R′ = (C1-C8) alkyl, (C7-C19) aralkyl or (C6-C18) aryl R = cyclohexyl or (C6-C18) aryl R′ = (C1-C8) alkyl, H, polymer linker or molecular weight enlarging polymer R″ H, polymer linker or molecular weight enlarging polymer X = NR′2, NR′H, OMe or OAc Y = PR2 or H R = cyclohexyl or (C6-C18) aryl R′ = (C1-C8) alkyl, (C6-C18) aryl or H R″ = polymer linker or molecular weight enlarging polymer n = 0, 1 or 2 R = H, (C1-C8) alkyl, polymer linker or molecular weight enlarging polymer R = cyclohexyl or (C6-C18) aryl R′ = H, C1-C8) alkyl or (C6-C18) aryl R = (C1-C8) alkyl R′ = H, O—(C1-C8) alkyl, O—(C7-C19) aralkyl, O—(C6-C18) aryl or OH R = cyclohexyl, (C6-C18) aryl R′ = H, polymer linker or molecular weight enlarging polymer R = cyclohexyl or (C6-C18) aryl R′ = H, polymer linker or molecular weight enlarging polymer R = H, (C1-C8) alkyl, (C7-C19) aralkyl, polymer linker or molecular weight enlarging polymer R = cyclohexyl or (C6-C18) aryl R′ = H, (C1-C8) alkyl, polymer linker or molecular weight enlarging polymer R″ H, (C1-C8) alkyl (C7-C19) aralkyl, (C6-C18) aryl, polymer linker or molecular weight enlarging polymer R = cyclohexyl or (C6-C18) aryl R′ = H, (C1-C8) alkyl, (C7-C19) aralkyl, (C6-C18) aryl, polymer linker or molecular weight enlarging polymer R = cyclohexyl or (C6-C18) aryl X = CH2, O, S, PR or NH R = H, polymer linker or molecular weight enlarging polymer R = H, polymer linker or molecular weight enlarging polymer (n = 1-6) R = (C1-C8) alkyl, (C7-C19) aralkyl, (C6-C18) aryl, polymer linker or molecular weight enlarging polymer R = cyclohexyl, (C6-C18) aryl R′ H, (C1-C8) alkyl, (C7-C19) aralkyl, (C6-C18) aryl, polymer linker or molecular weight enlarging polymer n = 0-5 n = 0 or 1 R = (C1-C8) alkyl or H R′ = H, (C1-C8) alkyl, (C7-C19) aralkyl, (C6-C18) aryl, polymer linker or molecular weight enlarging polymer R = (C1-C8) alkyl or (C6-C18) aryl, n = 0-5 R = (C1-C8) alkyl, (C7-C19) aralkyl or (C6-C18) aryl R = cyclohexyl or (C6-C18) aryl R′ = (C1-C8) alkyl, (C6-C18) aryl, polymer linker or molecular weight enlarging polymer R″ = H, (C1-C8) alkyl, (C7-C19) aralkyl, (C6-C18) aryl, polymer linker or molecular weight enlarging polymer OR′, OAc, NR′2 or NH2 R = cyclohexyl or (C6-C18) aryl R′ = (C1-C8) alkyl, (C6-C18) aryl polymer linker or molecular weight enlarging polymer R″ = H, (C1-C8) alkyl, (C6-C18) aryl, OR″, OAc, NR′2, NH2, polymer linker or molecular weight enlarging polymer R = O, S, NH R′ = H, (C1-C8) alkyl, (C7-C19) aralkyl or (C6-C18) aryl, polymer linker or molecular weight enlarging polymer R″ = (C1-C8) alkyl, (C7-C19) aralkyl, (C6-C18) aryl R = (C1-C8) alkyl, (C7-C19) aralkyl or (C6-C18) aryl R = (C1-C8) alkyl, (C7-C19) aralkyl or (C6-C18) aryl R″ = (C1-C8) alkyl, (C7-C19) aralkyl or (C6-C18) aryl R = polymer linker or molecular weight enlarging polymer or H R′ = (C1-C8) alkyl, (C7-C19) aralkyl, (C6-C18) aryl polymer linker or molecular weight enlarging polymer Bis(3,4-diarylphosphinyl)pyrrolidine
• wherein a line extending from said formulas of said active center represents a bond of a binding site both for the molecular weight enlarging polymer or for the optional polymer linker;
• wherein said polymer linker is a member selected from the group consisting of formulae a)-g):
• a) —Si(R2)— b) —(SiR2—O)n— n = 1-10000;
• c) —(CHR—CHR—O)n— n = 1-10000;
• d) —(X)n— n = 1-20;
• e) Z—(X)n— n = 0-20;
• f) —(X)n—W n = 0-20;
• and g) Z—(X)n—W n = 0-20;
• wherein
• R is H, (C1-C8) alkyl, (C6-C18) aryl, (C7-C19) aralkyl, or ((C1-C8) alkyl)1-3-(C6-C18) aryl;
• X is (C6-C18) arylene, (C1-C8) alkylene, (C1-C8) alkenylene, ((C1-C8) alkyl)1-3-(C6-C18) arylene, or (C7-C19) aralkylene;
• Z is C(═O)O—, C(═O)NH—, C(═O)—, NR, O, CHR, CH2, C═S, S, PR, Z being bound directly to said molecular weight enlarging polymer;
• and
• W is C(═O)O—, C(═O)NH—, C(═O)—, NR, O, CHR, CH2, C═S, S, PR, W being bound directly to said active center;
• wherein the molecular weight-enlarging polymer is a member selected from the group consisting of polyacrylates, polyvinylpyrrolidinones polysiloxanes, polybutadienes, polyisoprenes, polyalkanes, polystyrenes, polyoxazolines and mixtures thereof.