Organic compounds
AssigneeGivaudan SA
InventorsRoger Wilhelm GEISSER, Jürg Daniel OETIKER, Fridtjof SCHRÖDER
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Abstract
A process for the hydrogenation of a substrate comprising a carbon heteroatom double bond in the presence of a transition metal complex comprising a tridentate or bisdentate-ligand containing a nitrogen, sulphur and phosphorus atom, of which at least the N- and P- and optionally also the S-atom coordinates with the transition metal.
Claims17
A process for the hydrogenation of a functional group containing a carbon heteroatom double bond, in the presence of a transition metal complex according to the general formula
- MX2[SNP]Y
- wherein M is a group VIII transition metal and SNP represents a tridentate or bisdentate ligand containing a nitrogen, sulphur and phosphorus atom, of which at least the N- and P- and optionally also the S-atom coordinates with the transition metal, each X is independently selected from a halide, hydroxyl, alkoxy, acyloxy or amido;
- and each Y is independently selected from a phosphine or a carbon monoxide (CO) ligand, a nitrosyl group or a RCN group, wherein R is alkyl or aryl.
A process according to any of the preceding claims wherein the tridentate or bisdentate ligand is represented by the formula
- wherein
- R1 and R2 are independently selected from H, or C1 to C20 alkyl or aryl, which may be substituted or unsubstituted, or R1 and R2 are connected such that together with the sulphur and carbon atoms to which they are attached, they form a heteroaliphatic or heteroaromatic ring, which may be substituted or unsubstituted, and wherein if the ring is heteroaromatic it is not a 5-membered heterocycle containing both S and N heteroatoms, such as a thiazole;
- R3 through R7 are independently selected from H or C1 to C20 linear or branched alkyl group or alkenyl group;
- C3 to C8 cyclic alkyl group;
- or a C5 to C10 aryl group, wherein any of the foregoing groups may be substituted or unsubstituted;
- or R2 and R3;
- R3 and R4;
- or R2 and R4, together with the carbon atoms to which they are attached form a 5- or 6-membered aliphatic ring, which is optionally unsaturated;
- and/or R5 and R6;
- R5 and R7;
- or R6 and R7, together with the carbon atoms to which they are attached form a 5- or 6-membered aliphatic ring, which is optionally unsaturated;
- R8 and R9 independently are selected from H or C1 to C20 linear or branched alkyl group or alkenyl group;
- C3 to C8 cyclic alkyl group;
- a C5 to C10 aryl or heteroaryl group;
- a and b are independently 0, 1 or 2;
- n is 0 or 1;
- and
- represents a single or a double bond, provided that when R2 is H or C4 to C20 alkyl, represents a single bond;
- and when n is 1 each N represents a carbon-nitrogen single bond;
- whereas when n is 0, one N is a carbon-nitrogen single bond and the other N is a carbon-nitrogen double bond.
A process according to any of the preceding claims wherein the tridentate or bisdentate ligand in represented by the formula selected from the group consisting of
- wherein
- R10 is optionally substituted C1-10 alkyl, aryl, heteroaryl, alkenyl, nitrile and halide, and
- m is 0, 1, 2 or 3.
A process according to any of the preceding claims wherein the metal M is ruthenium or osmium.
A process according to any of the preceding claims wherein the functional group that is hydrogenated is selected from the group consisting of an ester, lactone, ketone, aldehyde, amide, lactam and imine.
A process according to any of the preceding claims wherein the substrate bearing a functional group containing a carbon heteroatom double bond is sclareolide and the hydrogenated product is sclareodiol.
A transition metal complex according to the general formula
- MX2[SNP]Y
- wherein M is a group VIII transition metal and SNP represents a tridentate or bisdentate-ligand containing a nitrogen, sulphur and phosphorus atom, of which at least the N- and P- and optionally also the S-atom coordinates with the transition metal, each X is independently selected from a halide, hydroxyl, alkoxy, acyloxy or amido;
- and each Y is independently selected from a monodentate phosphine or a carbon monoxide (CO) ligand, a nitrosyl group or a RCN group, wherein R is alkyl or aryl.
A complex according to any of the preceding claims wherein the tridentate or bisdentate ligand is represented by the formula
- wherein
- R1 and R2 are independently selected from H, or C1 to C20 alkyl or aryl, which may be substituted or unsubstituted, or R1 and R2 are connected such that together with the sulphur and carbon atoms to which they are attached, they form a heteroaliphatic or heteroaromatic ring, which may be substituted or unsubstituted;
- R3 through R7 are independently selected from H or C1 to C20 linear or branched alkyl group or alkenyl group;
- C3 to C8 cyclic alkyl group;
- or a C5 to C10 aryl group, wherein any of the foregoing groups may be substituted or unsubstituted;
- or R2 and R3;
- R3 and R4;
- or R2 and R4, together with the carbon atoms to which they are attached form a 5- or 6-membered aliphatic ring, which is optionally unsaturated;
- and/or R5 and R6;
- R5 and R7;
- or R6 and R7, together with the carbon atoms to which they are attached form a 5- or 6-membered aliphatic ring, which is optionally unsaturated;
- R8 and R9 independently are selected from H or C1 to C20 linear or branched alkyl group or alkenyl group;
- C3 to C8 cyclic alkyl group;
- a C5 to C10 aryl or heteroaryl group;
- a and b are independently 0, 1 or 2;
- n is 0 or 1;
- and
- represents a single or a double bond, provided that when R2 is H or C4 to C20 alkyl represents a single bond;
- and when n is 1 each N represents a carbon-nitrogen single bond;
- whereas when n is 0, one N is a carbon-nitrogen single bond and the other N is a carbon-nitrogen double bond.
A tridentate or bisdentate ligand L presented by the formula
- wherein
- R1 and R2 are independently selected from H, or C1 to C20 alkyl or aryl, which may be substituted or unsubstituted, or R1 and R2 are connected such that together with the sulphur and carbon atoms to which they are attached, they form a heteroaromatic or heteroaliphatic ring, which may be substituted or unsubstituted, and wherein said heteroaromatic ring is not a 5-membered heterocycle containing both S and N atoms;
- R3 through R7 are independently selected from H or C1 to C20 linear or branched alkyl group or alkenyl group;
- C3 to C8 cyclic alkyl group;
- or a C5 to C10 aryl group, wherein any of the foregoing groups may be substituted or unsubstituted;
- or R2 and R3;
- R3 and R4;
- or R2 and R4, together with the carbon atoms to which they are attached form a 5- or 6-membered aliphatic ring, which is optionally unsaturated;
- and/or R5 and R6;
- R5 and R7;
- or R6 and R7, together with the carbon atoms to which they are attached form a 5- or 6-membered aliphatic ring, which is optionally unsaturated;
- R8 and R9 independently are selected from H or C1 to C20 linear or branched alkyl group or alkenyl group;
- C3 to C8 cyclic alkyl group;
- a C5 to C10 aryl or heteroaryl group;
- a and b are independently 0, 1 or 2;
- n is 0 or 1;
- and
- represents a single or a double bond, provided that when R2 is H or C4 to C20 alkyl, represents a single bond;
- and when n is 1 each N represents a carbon-nitrogen single bond;
- whereas when n is 0, one N is a carbon-nitrogen single bond and the other N is a carbon-nitrogen double bond;
- with the proviso that the ligand L is not
Dependencies are inferred from the claim text.