Title of Invention

ASYMMETRIC HYDROGENATION OF ALKENES USING CHIRAL IRIDIUM COMPLEXES

Abstract

The invention relates to the (stereoselective) hydrogenation of carbon-carbon double bonds in compounds having at least one such bond, e.g., isoprenoids, non-cyclic sesquiterpenes, tocomonoenols, tocodienols, tocotrienols or derivatives thereof, as well as to the (stereoselective) hydrogenation of parts/extracts of plant oils containing such tocotrienols or derivatives thereof, in the presence of a chira! Ir complex as the catalyst, whereby preferably one stereoisomer is manufactured in an excess.

Full Text

ASYMMETRIC HYDROGENATION OF ALKENES USING CHIRAL IRIDIUM COMPLEXES The present invention relates to the (stereoselective) hydrogenation of a compound of the formula II with at least one carbon-carbon double bond, especially to the (stereoselective) hydrogenation of isoprenoids, non-cyclic sesquiterpenes, tocomonoenols, tocodienols, tocotrienols or any derivatives thereof, as well as to the (stereoselective) hydrogenation of parts/extracts of plant oils containing such tocotrienols or derivatives thereof, in the presence of a chiral Ir complex as the catalyst, whereby preferably one stereoisomer is manufactured in an excess. In the prior art there exists no general method for the asymmetric hydrogenation of trisubstituted olefins bearing no functional group in near proximity, that means olefins in which the carbon atoms of the olefinic double bond are spaced from the functional group(s) by two or more CH2-groups could not be stereoselective hydrogenated so far. A "functional group" is understood as a group consisting of an aromatic residue or groups containing heteroatoms like O, N, S, P or similar. Examples of corresponding compounds which are useful for the synthesis of optically active tocopherols (vitamin E) are tocotrienols, unsaturated isoprenoids like geranylacetone or farnesene acid alkyl esters. Therefore, there is a need to provide catalysts for such stereoselective hydrogenation. Surprisingly it was found that chiral Ir complexes, especially those containing P-N ligand systems, are suitable for that purpose. Such catalysts were until now only known for the stereoselective hydrogenation of aromatic compounds (see A. Pfaltz et al., Adv. Synth. Catal. 2003, 345 (1 + 2), 33-43; F. Menges, A. Pfaltz, Adv. Synth. Catal. 2002, 344 (1), 40-44; J. Blankenstein, A. Pfaltz, Angew. Chem. Int. Ed. 2001,40 (23), 4445-4447; A. Pfaltz, Chimia2004, 58 (1 + 2), 49-50). Thus, one aspect of the invention refers to a process for the manufacture of at least one compound of the formula I (Formula Removed) wherein the position labelled with the asterisk is an asymmetry center and R1 is selected from the group consisting of linear C1-3~alkyl, C5-7-cycloalkyl, hydroxyl, hydroxyallcyl (alkyl = C1-4-alkyl), oxoalkyl (alkyl = C1-4-alkyl), alkylcarbonyl (alkyl = alkyl), alkoxycarbonyl (alkoxy = linear C1-4-alkoxy) and a group of the formula (Formula Removed) with R2 being a hydroxyl group or a protected hydroxyl group, and R3 and R4 being independently from each other hydrogen or methyl, and n being an integer from 1 to 10, preferably from 1 to 3, comprising the step of hydrogenating a compound of the formula II (Formula Removed) wherein at least one carbon-carbon double bond is present, and wherein the dotted lines represent the possible positions of such (facultative) carbon-carbon double bonds; and R1 and n are as above, in the presence of a chiral Ir complex as the catalyst. Preferably in such process one stereoisomer of the compound I is manufactured in excess. If a compound of formula n with only one prochiral center is used preferably one enantiomer is manufactured in excess. The stereoselectivity of the hydrogenation can be controlled by appropriate choive of the catalyst. Starting material Examples of the compounds of the formula II are those presented in Fig. 4: Hal = (E)-Dihydrogeranylacetone, IIa2 = (Z)-dihydronerylacetone, IIa3 = (E)-geranylacetone, IIa4 - (Z)-nerylacetone, IIb = (all-E)-farnesol; IIc = (all-E)-farnesene acid ethyl ester, (S)-XII = (2S,3'E,7'E)-tocotrienol and derivatives thereof, (R)-XII = (2R,3'E,7'E)-tocotrienoi and derivatives thereof, (S)-XIII = (2S,3'E,7'E)-tocomono- and -dienols with the dotted lines indicating the possible positions of the one or two double bond(s), (R)-XIII = (2R,3'E,7'E)-tocomono- and -dienols with the dotted lines indicating the possible positions of the one or two double bond(s). (Table Removed) Preferably the compound of the formula n is an isoprenoid, a non-cyclic sesquiterpene, a tocomonoenol, a tocodieno] or a tocotrienol. An isoprenoid is an oligo(isoprene) or a poly(isoprene) and derivatives thereof which contain at least one carbon-carbon double bond. Preferably the carbon-carbon double bond has the E configuration. The tocomonoenol, the tocodienol and/or the tocotrienol is of the formula XIII, (Table Removed) wherein the dotted bonds are optional and at least one of the dotted bonds is present, and wherein R2 is a hydroxyl group or a protected hydroxyl group and R3 and R4 are independently from each other hydrogen or methyl. Compound XBI thus encompasses (3'E)-tocomonoenols, (7'E)-tocomonoenols, (11 ')-tocomonoenols, (3'E,7'E)-tocodienols, (3'E,ll')-tocodienols, (7'E,ir>tocodienols, as well as (3'E,7'E)-tocotrienols. Concerning the substituent R2 in formulae L II and XIII R2 is a hydroxyl group or a protected hydroxyl group. The hydroxyl group can be protected as ether, ester, or acetal. Examples of ethers and acetals are the methylether, the methoxyrnethylether, the methoxyethylether and the tetrahydropyranyl ether, as well as compounds where R is ethoxyethyl or methoxyethoxyethyl. Examples of esters are the acetic acid ester and esters with other carbonic acids such as formic acid ester, succinic acid monoester (or derivatives), propionic acid ester, benzoic acid ester and palmitic acid ester. Preferably R2 is a protected hydroxyl group, whereby the hydroxyl group is protected as ether or ester, more preferably as ester, especially preferably R2 is acetyloxy. In another aspect the present invention is also concerned with a process for the manufacture of a hydrogenated part or extract of a plant oil, preferably of palm oil, comprising the step of hydrogenating the part or extract of the plant oil comprising at least a tocotrienol or derivative thereof in the presence of a chiral IR complex as the catalyst. That means in the present invention such "a part or extract of the plant oil comprising at least a tocotrienol or derivative thereof is also encompassed by the term "compound of the formula n with at least one carbon-carbon double bond". The expression "part of a plant oil" encompasses any untreated or treated part of the plant oil, any concentrated part as well as the whole plant oil itself, "treated" means chemically treated such as distilled or extracted or thermally treated. Preferably the edible plant oil is treated in such a way that a part is obtained where the tocotrienols originally contained in the edible plant oil are enriched ("concentrate"). This part of the edible plant oil can be per se not edible. Examples of plant oils are any edible plant oils known to the person skilled in the art. Especially preferred is palm oil which contains beside small amounts of a- and γ-tocopherol large amounts of tocotrienols. In a preferred embodiment of the invention the tocotrienol or the derivative thereof is hydrogenated to a tocopherol (derivative), preferably to a highly stereoisomerically enriched (all-R)-tocopherol (derivative). Catalyst Suitable catalyst for the process of the present invention are Ir complexes with chiral organic ligands, especially those disclosed by A. Pfaltz et al. in Adv. Synth. Catal. 2003, 345 (1 + 2), 33-43; by F. Menges and A. Pfaltz in Adv. Synth. Catal. 2002,344 (1), 40-44;by J. Blankenstein and A. Pfaltz in Angew. Chem. Int. Ed. 2001, 40 (23), 4445-4447, by A. Pfaltz in Chimia 2004, 58 (1 + 2), 49-50 and in US 6,632,954. Suitable catalysts are especially the Ir complexes of the formula III, IV, V, VI, VE, VEI, DC, X, XI or XV and their enantiomers (Formula Relmoved) wherein R, X1, X2, X3, X4, X5, X6, X7, X8, X9,X10, X11, X12, X13, X14, X15, X16, X17, X18, X19,X20 ,X2! and X22 are independently from each other hydrogen, C1-4-allcyl, C5-7-cycloalkyl, phenyl (optionally substituted with one to three C1-4-alkyl, C1-4-alkoxy and/or C1-4 perfluoroalkyl groups), benzyl, 1-naphthyl, or ferrocenyl, the anion Y is a low coordinating anion, n is 1 or 2, and wherein "o-Tol" means ortho-tolyl, "Ph" means phenyl, "TBDMS" means tert-butyl-di-methylsilyl, "p-Tol" means para-tolyl, and "BArF" means tetra(3,5-bis(trifluoromethyl)-phenyl)borate. Suitable catalysts are also the corresponding Ir complexes and their enatiomers, in which the cyclooctadiene ligand is replaced by olefins, e.g. ethene, norbornadiene. Preferred chiral Ir complexes suitable for the process of the present invention are Ir complexes of the formulae IH to XI, wherein R,X1,X2,X3,X4,X5,X6,X7,X8,X9,X10,X11,X12,X13,X14,X15,X16,X17,X18,X19,X20,X21 and X22 are independently from each other hydrogen, Ci-4-alkyl, Cs-v-cycloalkyl, phenyl (optionally substituted with one to three C1-4-alkyl, C1-4-alkoxy and/or C1-4 perfluoroalky] groups), benzyl, 1-naphthyl, or ferrocenyl, and the anion Y is a weakly coordinating anion such as PF6", SbF6", BArF", BF4, F3, SO3 C1O4, tetra(perfluoroaryl)borate or tetra(perfluoroalkyloxy)alimiinate whereby the perfluoroaryl is a phenyl substituted with 1 to 5 perfluoro-C1-4-alkyl groups and the per-fluoroalkyloxy has 1 to 4 carbon atoms. Especially preferred are Ir complexes of the formulae IE to XI and XV, wherein XR,X1,X2,X3,X4,X5,X6,X7,X8,X9,X10,X11,X12,X13,X14,X15,X16,X17,X18,X19,X20,X21 and X22 and X22 are independently from each other hydrogen, methyl, ethyl, iso-propyl, n-butyl, iso-butyl, tort-butyl, cyclohexyl, phenyl, benzyl, o-tolyl, m-tolyl, 4-methoxyphenyl, 4-trifluoromethylphenyl, 3,5-di-tert-butylphenyl, 3,5-dimethoxyphenyl, 1-naphthyl, or ferrocenyl, and the anion Y is tetra(perfluoroaryl)borate or tetra(perfluoroalkyloxy)aluminate whereby the perfluoroaryl is a phenyl substituted with 1 to 3 perfluoro-C1-4 alkyl groups and the per-fluoroalkyloxy has 1 to 4 carbon atoms. More preferred chiral Ir complexes suitable for the process of the present invention are Ir complexes of the formulae III to XI, and XV, wherein R, X5, X14 and X20, X21, and X22 are independently from each other hydrogen, iso-propyl, tert-butyl, phenyl, 3,5-di-tert-burylphenyl or ferrocenyl, X1 and X2, as well as X7 and X8, as well as X9 and X10 and X15 and X16 are independently from each other phenyl, o-tolyl, cyclohexyl or iso-propyl, preferably X1 and X2 as well as X7 and X8 or X9 and X10 or X15 and X16 are the same, X3 and X4 as well as X1' and X12 as well as X17 and X18 are independently from each other methyl, ethyl, n-butyl, iso-butyl or benzyl, preferably X3 and X4, X11 and X12, X17 and X18 are the same, X6 is hydrogen or methyl, X13 and X19 are independently from each other phenyl, cyclohexyl, 4-methoxyphenyl, 3,5-dimethoxyphenyl, 4-trifluoromethylphenyl, benzyl, m-tolyl or 1-naphthyl, Y is tetra(3,5-bis(trifluoromethyl)phenyl)borate [B(3,5-C6H3(CF3)2)4]" or tetra(perfluorotert-butyloxy)aluminate [A1(OC(CF3)3)4J" and n is as defined earlier. Even more preferred chiral Ir complexes suitable for the process of the present invention are Ir complexes of the formulae II to XI, and XV, wherein R is hydrogen, iso-propyl or tert-butyl, X1 and X2 are independently from each other phenyl, o-tolyl, cyclohexyl or iso-propyl, preferably X1 and X2 are the same, X3 and X4 are independently from each other benzyl or iso-butyl, preferably X3 and X4 are the same, X5 is phenyl, 3,5-di-tert-butylphenyl or ferrocenyl, X6 is hydrogen or methyl, X7 and X8 are independently from each other phenyl or cyclohexyl, preferably X7 and X8 are the same, X9 and X10 are independently from each other phenyl or o-tolyl, preferably X9 and X10 are the same. X11 and X12 are independently from each other methyl, ethyl or n-butyl, preferably X11 and X12 are the same, X13 is phenyl, cyclohexyl, 4-methoxyphenyl, 3,5-dimethoxyphenyl, 4-trifluoromethylphenyl, benzyl, m-tolyl or 1-naphthyl, X14 is iso-propyl or tert-butyl, X15 and X16 are independently from each other phenyl or o-tolyl, preferably X15 and X16 are the same, X17 and X18 are independently from each other methyl or n-butyl, preferably X17 and X18 are the same, X19 is phenyl or 1-naphthyl, X20 is iso-propyl or tert-buryl, X21 and X22 are Y istetra(3,5-bis(trifiuoromethyl)phenyl)borate [B(3,5-C6H3(CF3)2)4]~ or tetraperfluorotert-bulyloxyaluminate [A1(OC(CF3)3)4]~ and n is as defined earlier. The most preferred chiral Ir complexes suitable for the process of the present invention are the Ir complexes of the formulae in to XI presented in the Fig. 1 to 3. Hereby the following abbreviations are used hi the formulae: "Cy" = cyclohexyl, "Bn" = benzyl, "i-Bu" = iso-butyl, "n-Bu" = n-butyl,, "t-Bu" = tert-buryl, "Fc" = ferrocenyl, "o-Tol" = o-tolyl, "p-Tol" = p-tolyl, "i-Pr" = iso-propyl, "Me" = methyl, "Ph" = phenyl, "TBDMS" = tert-butyl-dimethyl silyl, "BArp' is tetra(3,5-bis(trifluoromethyl)phenyl)borate[B(3,5-C6H3(CF3)2)4]~. Fig. 1 shows preferred Ir complexes of the formula DI (Al, A2, A4, A5, Gl) and IV (Cl, C2, C5, C6). Fig. 2 shows preferred Ir complexes of the formulae VII (El and E3 to E14). Fig. 3 shows the Ir complexes of the formulae V (Bl), VI (Dl), VEt (E2, E15), DC (Fl), X (C4), XI (B2) and XV (HI). Reaction conditions In the hydrogenation process of the present invention the amount of the catalyst is conveniently from about 0.05 to about 5 mol %, preferably from about 0.09 to about 2.5 mol %, more preferably from about 0.1 to about 2.0 mol-%, based on the amount of the compound of the formula II. Preferred examples of halogenated aliphatic hydrocarbons are mono- or polyhalogenated linear, branched or cyclic C1- to C15-alkanes. Especially preferred examples are mono- or polychlorinated or -brominated linear, branched or cyclic d- to C15-alkanes. More preferred are mono- or polychlorinated linear, branched or cyclic C1- to C15-alkanes. Mostpreferred are dichloromethane, 1,2-dichloroethane, toluene 1,1,1-trichloroethane, chloroform, and methylene bromide. Further, toluene, benzene, and chlorobenzene come into consideration. The reaction may be carried out under solvent free conditions, or in presence of one or more of the solvents mentioned above. The concentration of the reactants in the solution is not critical. The reaction is conveniently carried out at an absolute pressure of hydrogen from about 1 to about 100 bar, preferably at an absolute pressure of hydrogen from about 20 to about 75 bar. The reaction temperature is conveniently between about 0 to about 100°C, preferably between about 10 to about 40°C. The sequence of addition of the reactants and solvent is not critical. Preferred embodiments of the invention In a first preferred embodiment of the present invention, (Z)-nerylacetone or (E)-geranylacetone or any mixture thereof is hydrogenated in the presence of a chiral Ir complex selected from the group consisting of catalyst A2 (see Fig. 1), Dl (see Fig. 3), Bl (see Fig. 3) and El (see Fig. 2), preferably in the presence of a chiral Ir complex selected from the group consisting of catalyst Dl, Bl and El, more preferably in the presence of a chiral Ir complex selected from the group consisting of catalyst Bl and El to form a mixture of the enantiomers (6S)-6,10-dimethylundecane-2-one and (6R)-6,10-dimethyhmdecane-2-one. Preferably the hydrogenation is stereoselective in that way that one enantiomer is present in the mixture in an enantiomeric excess, preferably of at least 84%, more preferably of at least 90%. In a second preferred embodiment of the present invention (E)-farnesol is hydrogenated in the presence of the chiral Ir complex El (see Fig. 2) or Bl (see Fig. 3) to form a mixture of two enantiomeric pairs (3R,7S)-3,7,ll-trimethyldodecane-l-ol and (3S,7R)-3,7,11-trimethyldodecane-1-ol as well as (3R,7R)-3,7,ll-trimethyldodecane-l-ol and (3S.7S)-3,7,11-trimethyldodecane-l-ol. Hereby preferably the stereoisomer (3S,7S)-3,7,11-trimethyldodecane-1 -ol is present in the mixture obtained after the hydrogenation in an excess compared to the other stereoisomers, preferably in an amount of at least 70%, more preferably in an amount of at least 75%. In a third preferred embodiment of the present invention (E)-farnesene acid ethyl ester is hydrogenated in the presence of the chiral Ir complex Bl (see Fig. 3) or El (see Fig. 2) to form a mixture of two enantiomeric pairs (3R,7S)-3,7,11 trimethyldodecanoic acid ethyl ester and (3S,7R)~3,7,11- trimethyldodecanoic acid ethyl ester as well as (3R,7R)-3,7,11-trimethyldodecanoic acid ethyl ester and (3S,7S)-3,7,11- trimethyldodecanoic acid ethyl ester. Hereby the hydrogenation is preferably stereoselective in that way that the stereoisomer (3S,7S)-3,7,11- trimethyldodecanoic acid ethyl ester is manufactured -compared to the other stereoisomers - in an excess, preferably in an amount of at least 55%, more preferably in an amount of at least 70%. In a fourth preferred embodiment of the present invention (2R,3'E,7'E)-a-tocotrienyl acetate is hydrogenated in the presence of the chiral Ir complex El (see Fig. 2), E2 (see Fig. 3), E7 (see Fig. 2)or El 5 (see Fig. 3) to form a mixture of the four diastereoisomers (2R,4'S,8'R)-a-tocopheryl acetate, (2R,4'R,8'S)-a-tocopheryl acetate, (2R,4'R,8'R)-a-tocopheryl acetate and (2R,4'S,8'S)-α~tocopheryl acetate, wherein one diastereoisomer is manufactured in an excess. When the chiral Ir complex E2 or El5 (see Fig. 3) is used as the catalyst, the stereoisomer (2R,4'R,8'R)-a-tocopheryl acetate - compared to the other diastereoisomers - is manufactured in an excess, preferably in an amount of at least 55%, more preferably in an amount of at least 90%. hi a fifth preferred embodiment of the present invention (2S,3'E,7'E)-α-tocotrienyl acetate is hydrogenated in the presence of a chiral Ir complex selected from the group consisting of E3, E4, E6, E8, E9, El 0, El 1, E12, E13, E14 (all Fig. 2) as the catalyst, preferably in the presence of the chiral Ir complex El 3 or El 4 as the catalyst, to form a mixture of the four diastereoisomers (2S,4'S,8'R)-a-tocopheryl acetate, (2S,4'R,8'S)-a-tocopheryl acetate, (2S,4'R,8'R)-α-tocopheryl acetate and (2S,4'S,8'S)-α-tocopheryl acetate, whereby one diastereoisomer is manufactured in an excess. Preferably the diastereoisomer (2S,4'S,8'S)- a-tocopheryl acetate is manufactured in an excess - compared to the other diastereoisomers, preferably in an amount of at least 65%, more preferably in an amount of at least 85%. hi a sixth preferred embodiment of the present invention (2R,3'E,7'E)-y-tocotrienyl acetate is hydrogenated in the presence of the chiral Ir complex Cl (see Fig. 1), Dl (see Fig. 3), El (see Fig. 2) or Fl (see Fig. 3) as the catalyst, to form a mixture of the four diastereoisomers (2R,4'S,8'R)-y-tocopheryl acetate, (2R,4'R,8'S)-γ-tocopheryl acetate, (2R,4'R,8'R)-γ-tocopheryl acetate and (2R,4'S,8'S)-y-tocopheryl acetate whereby one diastereoisomer is manufactured in an excess. When the chiral Ir complex Fl is used as the catalyst, the diastereoisomer (2R,4'R,8'R)-a-tocopheryl acetate is manufactured in an excess -compared to the other diastereoisomers, preferably in an amount of at least 45%. Particular catalysts for use in the present invention are the chiral complexes represented by the formulae El to E15. Finally the present invention is also directed to the use of a chiral Ir complex, especially one of the formulae EL to XI as described above, as catalyst for the (stereoselective) hydrogenation of a compound selected from the group consisting of isoprenoids, non-cyclic sesquiterpenes, tocomonoenols, tocodienols and tocotrienols. Figures 1 to 5 Fig. 1 shows preferred Ir complexes of the formula in (Al, A2, A4, A5, Gl) and IV (Cl, C2, C5, C6). Fig. 2 shows preferred Ir complexes of the formulae VII (El and E3 to E14). Fig. 3 shows the Ir complexes of the formulae V (Bl), VI (Dl), VIE (E2, E15), IX (Fl), X (C4) and XI (B2). Fig. 4 shows examples of starting materials: IIal = (E)-Dihydrogeranylacetone, IIa2 = (Z)-dihydronerylacetone, IIa3 = (E)-geranylacetone, IIa4 = (Z)-nerylacetone, lib = (all-E)-farnesol; He = (all-E)-famesene acid ethyl ester, (S)-Xn = (2S,3'E,7'E)-tocotrienol and derivatives thereof, (R)-XII= (2R,3'E,7'E)-tocotrienol and derivatives thereof, (S)-XIII = (2S,3'E,7'E)-tocomono- and -dienols with the dotted lines indicating the possible positions of the one or two double bond(s), (R)-XIII = (2R,3'E,7'E)-tocomono- and -dienols with the dotted lines indicating the possible positions of the one or two double bond(s). Fig. 5 shows examples of products of the process of the present invention, whereby the asterisks indicate chirality centers:Ia= 6,10-dimethylundecane-2-one, Ib = 3,7,11-trimethyldodecane-1-ol, Ic = 3,7,11-trimethyldodecane acid ethyl ester, (2S)-XIV = (2S)-tocopherol and derivatives thereof, (R)-XIV = (2R)-tocopherol and derivatives thereof. (Table Removed) Examples The following abbreviations are used: "TLC" = thin layer chromatography; "GC" - gas chromatography; "GC-MS" = gas chromatography - mass spectrometry; "HPLC" = high pressure/performance liquid chromatography. The asterisks in the13C/lH-NMR parts mean that the signs could not be assigned unambiguously to a carbon/proton and the ones labelled with the asterisks are interchangeable. The enantiomeric excess concerning the S-enantiomer is calculated as follows [(amount of S-enantiomer minus amount of R-enantiomer)/(amount of S-enantiomer plus amount of R-enantiomer)] x 100. The enantiomeric excess concerning the R-enantiomer is calculated as follows [(amount of R-enantiomer minus amount of S-enantiomer)/(aniount of R-enantiomer plus amount of S-enantiomer)] x 100. | General remarks All starting materials were prepared by DSM Nutritional Products, Lalden/Sisseln, Switzerland: (E)-Geranylacetone, 99.2% (GC); (Z)-nerylacetone, 97.6% (GC); (E)-dihydrogeranylacetone, 99.2% (GC); (Z)-dihydronerylacetone, 98.9% (GC); (all-E)-farnesol, 97.7% (GC); (2E,6E)-farnesene acid ethyl ester, 99.0% (GC); (2E.6Z)- farnesene acid ethyl ester, 78.2% (GC), contains 1.4% of the (6E) isomer and 17.6% of another not known isomer (GC-MS); (R,E,E)-alpha-tocotrienol acetate, ca. 99%; (S,E,E)-alpha-tocotrienyl acetate, ca. 99%; (R,E,E)-gamma-tocotrienyl acetate (prepared by total synthesis) 99.7% (HPLC); (S,E,E)-gamma-tocotrienyl acetate (prepared by total synthesis), 99.8% (HPLC). Reference compounds: (all-rac)-alpha-Tocopherol, 99.6% (GC); (all-rac)-alpha-tocopheryl acetate, 97.7% (GC); (all-rac)-alpha-tocopheryl methyl ether, 97.8% (GC); (all-rac)-gamma-tocopherol, 96.8% (GC); (R,R,R)-gamma-tocopheryl acetate, ca. 99% (GC); (all-rac)-gamma-tocopheryl methyl ether, 97.9% (GC). If not stated otherwise, the GC analyses were performed with an Agilent 6890 GC FID on a CP-Sil-88 (Chrompack, Netherlands) 50m x 0.25mm column. The carrier gas was hydrogen with 90 kPa. The samples were injected as 0.3% solutions in dichloromethane with a split ratio of 1/30. The injector was held at 250°C whereas the oven temperature was programmed from 110-200°C at 0.5°C/min, the detector was at 250°C. In case of complete conversion a derivative of the hydrogenated product was prepared to determine the distribution of the stereoisomers. Hydrogenated ketones or aldehydes e.g. were reacted with L- or D -trimethylsilyl diisopropyltartrat (shortly "L-3", or "D-3") in the presence of trimethylsilyl triflate [Si(CH3)3(OSO2CF3)] to the diastereomeric ketals and acetals, respectively. With the aid of achiral gas chromatography the ratio of the diastereomers could be determined and thus the selectivity of the stereoselective hydrogenation determined indirectly. (See also A. Knierzinger, W, Walther, B. Weber, T. Netscher, Chimia 1989, 43,163-164; A. Knierzinger, W. Walther, B. Weber, R. K. Milller, T. Netscher, Helvetica Chimica Acta 1990,73,1087-1107) For the determination of the ratio of the diastereoisomers of the prepared tocopheryl acetates these were first reduced to the corresponding tocopherols with LiAlH4 and then reacted with dimethyl sulphate to the tocopheryl methyl ethers. There were obtained four diastereoisomers. Their ratio was determined via achiral gas chromatography. (See also W. Walther, T. Netscher, Chiraliry 1996, 8, 397-401.) The stereoisomeric composition of tocopherols (methyl ether derivatives) was also checked by chiral HPLC (Chiracel OD, 250 x 4.6 mm, solvent n-hexane, detection at 220 nm) in the case of the 2-(R)-isomers. If examples were carried out at "room temperature", this indicates that the reaction was carried out at a temperature of from about 20°C to about 30°C. Procedure 1 In an autoclave 0.25 mmol of the substrate, 1 mol-% of the Ir complex and 1.25 ml of absolute dichloromethane were put. The autoclave was closed and a pressure of 50 bar of hydrogen was applied. Under stirring the reaction solution was kept at room temperature for two hours. Afterwards the pressure was released and the solvent removed. For determining the conversion the raw product was analysed by GC without any further purification. If the reaction was complete, the product was converted into a derivative which enabled the determination of the stereoisomeric composition as illustrated further below in more detail, e.g., by converting a ketone to the (+)-L-diisopropyltartrate acetal and the (-)-D-diisopropyltartrate acetal, respectively. Examples 1 to 25: Preparation of 6.10-dimethylundecap-2-on The hydrogenation was carried out according to procedure 1, whereby 0.25 mmol of the substrate and 1 mol-% of the Ir-catalyst were used. The following substrates were used: (E)-Dihydrogeranylacetone [= (E)-6,10-dimethylundec-5-ene-2-one] (49.1 mg), (Z)-dihydronerylacetone [= (Z)-6,10-dimethylundec-5-ene-2-one] (49.1 mg), (E)- geranylacetone [= (E)-6,10-dimethylundeca-5,9-diene-2-one] (48.6 mg) or (2)-nerylacetone [= (2)-6,10-dimethylundeca-5,9-dien-2-on] (48.6 mg). 1H-NMR (400,1 MHz, CDC13) of the product: 5 = 0.85 (d, 3J = 6.6 Hz, 3 H, -CH(CH3)-), 0.86 (d, 3J = 6.6 Hz, 6 H, -CH(CH3)2), 1.10 (m, 4 H, 2 CH2), 1.26 (m, 4 H, 2 CH2), 1.39 (m, 1 H, CH), 1.54 (m, 3 H, CH2j CH), 2.13 (s, 3 Hs -C(O)-CH3), 2.40 (t, 3J = 7.6 Hz, 2 H, -C(O)-CH2~).— GC: Optima 5-Amin, 100 kPa He, temperature program: 100°C (3 min), 2°C/min, 155°C (0), 20°C/min, 250°C (5 min); solvent: ^-heptane; tR [la] = 27.3 min, tR [Eal] = 28.1 min, tR [Ha2] = 27.0 min, tR [3Ia3] = 30.3 min, tR [Ha4] = 29.2 min. The results are presented in the following tables 1 to 6: Table 1: Hydrogenation of (E)-dihydrogeranylacetone in dichloromethane (Table1 Removed) Table 2: Hydrogenation of (E) geranylacetone in dichloromethane (Table 2 Removed) Table._3: Hydxogenation of (Z)-dihydronerylacetone in dichloromethane (Table 3 Removed) Table_4: Hydrogenation of (Z)-nerylacetone in dichloromethane (Table 4 Removed) Table5 Hydrogenation of (E)-geranylacetone in dicnioromethane: Comparison of the reactivities of Ir-complex B 1 with different anion (Table 5 Removed) Table 6: Hydrogenation of (E)-geranylacetone in dicnioromethane: Optimization of the reaction conditions. (Table 6 Removed) xamples 26 to 33: Preparation of 3 ,7,11-trimethyldodecan-1-ol The hydrogenation was carried out according to procedure I, whereby 55.6 mg (0.25 mmol) of (2E,6E)-farneso! [= (2E,6E)-3,7,ll-Trimethyldodeca-2,6,10-trien-l-ol] and 1 mol-% of Ir catalyst were used. '1H-NMR (400.1 MHz, CDC13) of the product: 8 = 0.84 (d, 3J = 6.8 Hz, 3 H, *CH-CH3), 0.86 (d, 3J = 6.8 Hz, 6 H, CH(CH3)2), 0.89 (d, 3J = 6.6 Hz, 3 H, *CH-CH3), 1.0 - 1.42 (m, 14 H, 6 CH2, 2 CH), 1.55 (m, 3 H, CH2, CH), 3.68 (m, 2 H, CH2-OH).— GC: Restek Rtx-1701, 60kPaHe, temperature program: 50°C (0 min), 100C/min, 250°C (10 min); solvent: n-heptane; IR [3,7,11-trimethyldodecane-l-ol] = 18.5 min, tR [IIb] = 19.8 min. The results are presented in the following table 7: (Table7 Removed) The term "ee (3S)" denotes a value which is calculated for quantifying the extent of enantiomeric purity at C-3, omitting stereochemical information on C-7 as follows: ee (3S) = [(3S7R + 3S7S) minus (3R7S + 3R7R)] divided by [sum of all four stereoisomers (3S7R + 3S7S + 3R7S + 3R7R)]. The term "ee (7S)" denotes a value which is calculated for quantifying the extent of enantiomeric purity at C-7, omitting stereochemical information on C-3 as follows: ee (7S) = [(3S7S + 3R7S) minus (3R7R + 3S7R)] divided by [sum of all four stereoisomers (3S7S + 3R7S + 3R7R + 3S7R)]. Examples 34 to 39: Preparation of 3,7,1 l-trimethyl-dodecanoic acid ethyl ester The hydrgenation was carried out according to procedure 1, whereby 66.1 mg (0.25 mmol) of (2E,6E)-famesene acid ethyl ester [= (2E,6E)-3,7,ll-trimethyl-dodeca-2,6,10-triene acid ethyl ester] and 1 mol-% of the Ir-catalyst were used. 'H-NMR (400.1 MHz, CDC13): 8 = 0.84 (d, 3J = 6.6 Hz, 3 H, *CH-CH3), 0.86 (d, 3J = 6.6 Hz, 6 H, CH(CF3)2), 0.93 (d, 3J = 6.6 Hz, 3 H, *CH-CH3), 1.0-1.4 (m, 13 H, 6 CH2, CH(CH3)2), 1.25 (t, 3J = 7.0 Hz, 3 H, 0-CH2-CH3), 1.52 (m, 1 H, *CH), 1.94 (m, 1 H, *CH), 2.07 (ddt, 2J = 14.7 Hz, 3J = 8.1 Hz, 4J = 1.5 Hz, 1 H, CH2-COOEt), 2.28 (ddt, 2J = 14.7 Hz, 3J = 6.1 Hz, 4J = 1.8 Hz, 1 H, CH2-COOEt), 4.13 (q, 3J = 7.0 Hz, 2 H, O-Cff2-CH3).— GC: Restek Rtx-1701, 60 kPa He, temperature program: 50°C (0 min), 10°C/min, 250°C (10 min); solvent: n-heptane; tR [Ic] = 19.1 min, tR [IIc] = 21.0 min. The results are presented in the following table 8: (Table 8 Removed) The term "ee C-3 (S)" denotes a value which is calculated for quantifying the extent of enantiomeric purity at C-3, omitting stereochemical information on C-7 as follows: ee C-3 (S) = [(3S7R + 3S7S) minus (3R7S + 3R7R)] divided by [sum of all four stereoisomers (3S7R + 3S7S + 3R7S + 3R7R)]. The term "ee C-3 (R)" denotes a value which is calculated for quantifying the extent of enantiomeric purity at C-3, omitting stereochemical information on C-7 as follows: ee C-3 (R) = [(3R7R -+ 3R7S) minus (3S7S + 3S7R)] divided by [sum of all four stereoisomers (3R7R + 3R7S + 3S7S + 3S7R)]. The term "ee C-7 (S)" denotes a value which is calculated for quantifying the extent of enantiomeric purity at C-7, omitting stereochemical information on C-3 as follows: ee C-7 (S) = [(3S7S + 3R7S) minus (3R7R + 3S7R)] divided by [sum of all four stereoisomers (3S7S + 3R7S + 3R7R + 3S7R)]. The term "ee C-7 (R)" denotes a value which is calculated for quantifying the extent of enantiomeric purity at C-7, omitting stereochemical information on C-3 as follows: ee C-7 (R) = [(3S7R + 3R7R) minus (3R7S + 3S7S)] divided by [sum of all four stereoisomers (3S7R + 3R7R + 3R7S + 3S7S)], Procedure 2: Converting an ester such as 3,7,11-trimethyl-dodecanoic acid ethyl ester into a derivative for determination of the stereoisomeric composition 0.25 mmol of the isolated ester were dissolved in 2 ml of absolute tetrahydrofuran and mixed with 66 mg (1,75 mmol, 7 mol equivalents) of LiAULi. The grey suspension was stirred for one hour at room temperature, Afterwards 5 ml of destillated water were added under ice cooling and stirring was continued for another 10 minutes. The resulting phases were separated and the aqueous phase was extracted twice with diethyl ether. The combined organic extracts were dried over MgSO4 and the solvent was removed. The isolated alcohol, e.g., 3.7 J1 -trimethyldodecan-1 -ol was further reacted to the corresponding aldehyd, e.g., 3,7, 11 -trimethyl-dodecanal without any purification. Oxidation of 3,7,11-trimethyldodecane-1-ol to 3 7,11-trimethyl-dodecanal The isolated alcohol was dissolved under Ar atmosphere in 1 ml of absolute dichloromethane. 60 mg of pyridinium chlorochromate were added. The brown suspension was stirred until the turn-over was complete (ca. 3 hours) at room temperature. Then the suspension was diluted with 3 ml of diethyl ether and filtrated. The solvent was removed and the raw product purified by column chromatography on silica gel (solvent: diethyl ether), The solvent was removed. Thin layer chromatography: starting material: Rf-value = 0.22; product: Rf-value = 0.67 (SiOj, n-hexane/ethyl acetate (9:1); development with basic KMnO4 solution). For the preparation of the corresponding acetal the raw aldehyde was immediately further reacted. 1H-NMR (400.1 'MHz, CDC13): 8 = 0.84 (d, 3J = 6.6 Hz, 3 H, *CH-CH3), 0.86 (d, 3J = 6.6 Hz, 6 H, CH(CH3)2), 0.97 (d, 3J = 6.6 Hz, 3 H, *CH-CH3), 1.02 -1.42 (m, 13 H, 6 CH2, CH), 1.52 (m, 1 H, *CH), 1.96 (m, 1 H, *CH), 2.14 (ddd, 2J = 14.9 Hz, 3J = 5.8 Hz, 3J = 2.0 Hz, 1 H, -CH2-CHO), 2.35 (ddd, 2J = 14.9 Hz, 3J = 8.1 Hz, 3J = 2.0 Hz, 1 H, -CH2-CHO), 9.75(1,3J = 2.3 Hz, 1H, CHO), Acetalisation of 6.10-dimethylundecane-2-one to di-(2-methyl-ethyl)-('4R,5R)-2-[4,8-dimethylnonyl-2-methyl-1,3-dioxolane-4.5-dicarboxylate To 0.25 mmo] of (6R)-6,10-dimethylundecane-2-one and (6S)-6,10-dimethylundecane-2-one, respectively, were added 142 mg (0.38 mmol, 1.5 mol equivalents) of (2R,6R)-bissilylether (L-3) in 1 rnl of absolute dichloromethane under AT atmosphere. The reaction mixture was cooled to ~78°C. At this temperature 20 µL (0.1 mmol, 0.4 mol equivalents) of trimethylsilyl triflate were added. After 15 minutes the cooling bath was removed and the reaction mixture stirred for 12 hours at room temperature. Afterwards 0.14 ml (1.0 mmol) of triethyl amine were added and stirring continued for further 10 minutes. Then the solvents were removed in high vacuum. The residue was dissolved in diethyl ether, filtered over silica gel and the solvent evaporated. For determination of the diastereomeric excess the raw product was analyzed via GC without any further purification. TLC: Rf-value = 0.27 (SiO2, n-hexane/ ethyl acetate 9:1); Rr value (la) = 0.32.— GC: achiral column: CP-Sil-88 (50 m, 0.25 mm, 0.25µm), 100 % cyanopropylpolysiloxan; carrier gas: hydrogen (90 kPa); split injector (1:30), injection temperature: 250°C; FID detector, detection temperature: 250°C; temperature program: 147°C (isotherm); Solvent: dichloromethane; tR (4R,5R,4'S-acetal) = 129.3 min, tR (4R,5R,4'.R-acetal) = 130.7 min. 1H-NMR (400.1 MHz, CDC13): 8 = 0.84 (d, 3J = 6.6 Hz, 3 H, *CH-CH3), 0.85 (d, 3J = 6.6 Hz, 6 H, CH(CH3)2), 1.00 -1.57 (m, 12 H, 6 CH2), 1.29 (d, 3J = 6.3 Hz, 12 H, CO2CH(CH3)2), 1.44 (s, 3 H, acetal-CH3), 1.69 (m, 2 H, CH), 4.63 (d, 3J = 6.3 Hz, 1 H, *CH (tarrrate)), 4,67 (d, 3J = 6.3 Hz, 1 H, *CH (tartrate)), 5.13 (sept, 3J = 6.3 Hz, 2 H, 2 C02CH(CH3)2).— Acetalisation of 3,7,11-trimethyl-dodecane-1-carbaldehyde to di-(2-methylethyl)-(4R3R/4S,5S)(2,6,10-trirmethylundecyl]1-1.3-di-oxolan-4.5-dicarboxylate To 71 mg L-3 and D-3, respectively, were added under Ar atmosphere 0.5 ml of a solution of 0.25 mmol of freshly prepared 3,7,11-trimethyl-dodecane-l-carbaldehyde and 1.0 ml of absolute dichloromethane. The reaction mixture was cooled to -78°C. At this temperature 10 µL (0.05 mmol, 0.4 mol equivalents) of trimethylsilyl triflate were added dropwise. The further proceeding corresponds to the proceeding described above for the preparation of acetal of 6,10-dimethylundecane-2-one. TLC: Rf-value (product) = 0.25 (Si02, n-hexane/ ethyl acetate 9:1); Revalue (starting material) - 0.45.— GC: achiral column: CP-Sil-88 (50 m, 0.25 mm, 0.25 urn), 100% cyanopropylpolysiloxan; carrier gas: hydrogen (90 kPa), split injector (1:30), injection temperature: 250°C, FID detector, detection temperature: 250°C; temperature program: 110°C →200°C with a heating rate of 0.5°C/min; tR (L-Z'S^TJ-acetal) = 144.3 min, tR {(L-2'R,6'S- acetal) + (L-2'S,6'S~ acetal)} = 145.0 min, tR (L-2"R,6'R- acetal) = 145.6 min, or tR (D-2'R,6'S~ acetal) = 144.3 min, tR {(D-2'S,6'R- acetal) + (D-2'R,6'R- acetal)} = 145.0 min, tR (D-2'S,6'S- acetal) =145.6 min. 'H-NMR (400.1 MHz, CDC13): 6 = 0.83 (d, 3J = 6.6 Hz, 3 H, *CH-CH3), 0.86 (d, 3J = 6.8 Hz, 6 H, CH(CH3)2), 0.94 (d, 3J = 6.6 Hz, 3 H, *CH-CH3), 1.00 - 1.65 (m, 16 H, 7 x CH2, 2 x *CH), 1.28 (d, 3J = 6.3 Hz, 12 H, 2 C02CH(CH3)2), 4.56 (d, 3J = 4.3 Hz, 1 H, *CH (tartrate), 4.65 (d, 3J - 4.3 Hz, 1 H, *CH (tartrate), 5.11 (sept, 3J = 6.3 Hz; 1 H, C02CH(CH3)2), 5.12 (sept, 3J = 6.3 Hz, 1 H, C02CH(CH3)2), 5.30 (t, 3J = 5.05 Hz, 1 H, acetal-H).— Examples 40 to 68: Hydrogenation of tocotrienyl acetates Stereoselective hvdrogenation of (2R}- and (2S)-a-tocotrienvl acetate, as well as of (2R)-and (2S)-Y-tocotrienyl acetate Examples 40 to .6.1: Preparation of (2R)-α-tocopheryl acetate and f2S)-α-tocopheryl acetate Hydrogenation according to procedure 1, whereby 23.4 mg (0.05 mmol) of starting material and 1 mol-% of Ir catalyst (based on the amount of starting material) in 0.5 ml of absolute dichloromethane were used. Used starting materials: (2R,3'.E,7'.E')~α-tocotrienyl acetate, (2S',3'E',7'E)-a-tocotrienyl acetate. Determination of the turn-over via 1H-NMR; (2R/2S,3'E,7'E)- α-tocotrienyl acetate: 5.13 (m, 3 H, 3 alken-CH).— 'H-NMR (400.1 MHz, CD2C12): 6 = 0.87 (d, 3J = 6.6 Hz, 3 H, *CH-CH3), 0.88 (d, 3J = 6.6 Hz, 3 H, *CH-CH3); 0.89 (d, 3J = 6.6 Hz, 6 H, CH(CH3)2), 1.06 -1.63 (m, 21 H, 9 CH2, 3 CH), 1.26 (s, 3 H, 0-*C-CH3), 1.82 (m, 2 H, O-*C-CH2), 1.97 (s, 3 H, Ph-CH3), 2.01 (s, 3 H, Ph-CH3), 2.10 (s, 3 H, Ph-CH3), 2.31 (OC(0)CH3), 2.62 (m, 2 H, CH2 (cycl.)). The results are presented in the following tables 9,10, 11 and 12: Table 9: Hvdrogenation of (2S,3'EJ'E)-α-tocotrienyl acetate (Table 9 Removed) Table 10: Hydrogenation of (2R,3'E,7'E)-a-tocotrienyl acetate (Table 10 Removed) 5 Table 11: Hydrogenation of (2S,3'E,7'E)-α-tocotrienyl acetate (Table 11 Removed) If the catalyst E15 (enantiomer to Ir complex E14) was used (2R,3'E,7'E)-a-tocotrienyl acetat was hydrogenated to (2R,4'R,8'R)-tocopheryl acetate in a yield of 90% (see table 12). Table 12: Hydrogenation of (2R,3IE,7'E)-a-tocotrienyl acetate (Table 12 Removed) Examples 62 to 68: (2R)-γ-tocopheryl acetate and (2S)-γ-tocopheryl acetate Hydrogenation according to procedure 1, whereby 0.05 mmol (22.7 mg) of the starting material and 1 mol-% (based on the amount of starting material) of the Ir catalyst hi 0.5 ml of absolute dichoromethane were used. Used starting materials: (2R,3'E,7'E)-y-tocotrienyl acetate, (2S,3'E,7'E)-y-tocotrienyl acetate. The conversion was determined via 1H-NMR; (2R/2S,3'E,7'E)- y-tocotrienyl acetate: 5.13 (m, 3 H, 3 Alken-CH).— 1H-NMR (400.1 MHz, CD2C12): 5 = 0.86 (d, 3J = 6.6 Hz, 3 H, *CH-CH3), 0.87 (d, 3J = 6.6 Hz, 6 H, CH(OH3)2), 0.88 (d, 3J = 6.6 Hz, 3 H, *CH-CH3), 1.02 -1.68 (m, 21 H, 9 CH2,3 CH), 1.28 (s, 3 H, O-*C-CH3), 1.76 (dt, 2J = 13.5 Hz, 3J = 6.6 Hz, 1 H, 0-*C~CH2), 1.80 (dt, 2J = 13.5 Hz, 3J = 6.6 Hz, 1 H, 0-*C-CH2), 2.01 (s, 3 H, Ph-CH3), 2.12 (s, 3 H, Ph-CH3), 2.27 (s, 3 H, OC(O)CH3), 2.72 (ra, 2 H, CH2 (cycL), 6.56 (s, 1 H, ar. CH). The results are presented in the following tables 13 and 14: Table 13: Hydrogenation of (2S,3'E57'E)-y-tocotrienyl acetate (Table 13 Removed) Table 14: Hydrogenation of (2R,3'E,7'E)-γ-tocotrienyl acetate a) 4 mol% of the Ir-catalyst were used. (Table 14 Removed) For determination of the stereoisomeric composition the tocopheryl acetates were converted into tocopherols and tocopherol methyl ethers as follows: Reduction of the tocopheryl acetates to the corresponding tocopherols Preparation of (2R)-ot-tocopherol and (2S)-α-tocopherol Synthesis according to procedure 2, whereby 23.7 mg (0.05 mmol) of the starting material and 13 mg (0.35 mmol) of LiAlH4; were used in 1 ml of absolute tetrahydrofuran. Used starting materials: (2J?)~a-tocopheryl acetate and (2iS)-a-tocopheryl acetate. 'H-NMR (400.1 MHz, CD2C12): 8 = 0.86 (d, 3J = 6.6 Hz, 3 H, *CH-CH3), 0.87 (d, 3J = 6.6 Hz, 3 H, *CH-CH3), 0.88 (d, 3J = 6.6 Hz, 6 H, CH(CH3)2), 1-02 - 1.63 (m, 21 H, 9 CH2, 3 CH), 1.23 (s, 3 H, O-*C-CH3), 1 .79 (m, 2 H, O-*C-CH2), 2.10 (br s, 6 H, 2 Ph-CH3), 2.14 (s, 3 H, Ph-CH3)5 2.60 (m, 2 H, CH2 (cycl.)), 4.28 (br s, 1 H, OH). Preparation of (2R)-γ-tocopherol and (2s)-γ-tocopherol Synthesis according to procedure 2, whereby 22.9 mg (0.05 mmol) of starting material and 13 mg (0.35 mmol) of LiAlH4 were used in 1 ml of absolute tetrahydrofuran. Used starting materials: (2J?)-y-tocopheryl acetate and (25)-Y-tocopheryl acetate. 'H-NMR (400.1 MHz, CD2C12): 6 = 0.86 (d, 3J = 6.6 Hz, 3 H, 'CH-CHs), 0.87 (d, 3J = 6.6 Hz, 3 H, *CH-CH3), 0.88 (d, 3J = 6.6 Hz, 6 H, CH(CH3)2), 1.04 - 1.63 (m, 21 H, 9 CH2, 3 CH), 1.28 (s, 3 H, O-*C-CH3)5 1.75 (m, 2 H, O-*C-CH2), 2.09 (s, 3 H, Ph-CH3), 2.11 (s, 3 H, Ph-CH3), 2.67 (m, 2 H, CH2 (cycl.), 4.35 (br s, 1 H, OH), 6.36 (s, 1 H, ar. CH). Procedure 3 Preparation of the methyl ether of a- and γ-tocopherol 0.25 mmol of the isolated a- or y-tocopherol (raw product) were dissolved under an Ar atmosphere in 1 ml of absolute dimethoxyethan. 0.2 ml (2.5 mmol) of a 50 weight-% aqueous KOH solution were added dropwise. After stirring for 10 minutes 0.12 ml (1.25 mmol) of dimethyl sulfate were added dropwise. Afterwards the reaction mixture was stirred for one hour at room temperature. After complete turn-over the solvent was evaporated. The residue was stirred in 5 ml of distilled water and 10 ml of n-hexane for 5 minutes. The organic and the aqueous phase were separated. The aqueous phase was extracted with 10 ml of n-hexane. The combined organic phases were dried over MgS04 and the solvent evaporated. The obtained raw product was analyzed without any further purification via GC to determine the ratio of the diastereomers. Preparation of (2R)-α-tocopheryl methyl ether and (2S)-α-tocopheryl methyl ether Synthesis according to procedure 3; GC: achiral column: CP-Sil-88 (50 m, 0.25 mm, 0.25 pro), 100% cyanopropylpolysiloxane; carrier gas: hydrogen (90 kPa); split injector (1:30), injection temperature: 280°C; FID detector, detection temperature: 250°C; temperature program: 170°C (isotherm); solvent: ethyl acetate; tR of the products: tR (2R,4'R,8'S) = 144.5 min, tR (2R,4'R,8'R) = 146.2 min, tR (2R,4'S,VR) = 148.4 min, tR (2R,4'S,S'S) = 150.8 rnin bzw. tR (2S,4'S,8R) = 144.5 min, tR (2S,4'S,8'S) = 146.2 min, tR (2S,4'R8'S) = 148.4 min, tR (2S,4'R,8R) = 150.8 min. 1H-NMR (400.1 MHz, CD2C12): 5 = 0.86 (d, 3J = 6.6 Hz, 3 H, *CH-C#3), 0.87 (d, 3J = 6.6 Hz, 3 H, *CH-CH3), 0.88 (d, 3J = 6.6 Hz, 6 H, CH(CH3)2), 1-03 - 1.65 (m, 21 H, 9 CH2, 3 CH), 1.25 (s, 3 H, O-*C-CH3), 1.75 (m, 2 H, 0-*C-CH2), 2.09 (br s, 9 H, 3 Ph-CH3), 2.72 (m, 2 H, CH2 (cycl.), 3.74 (s, 3 H, -0-CH3). Preparation of (2R)-'γ-tocopheryl methyl ether and (2S)-γ-tocopheryl methyl ether Preparation according to procedure 3; GC: achiral column: CP-Sil-88 (50 m, 0.25 mm, 0.25 urn), 100% cyanopropylpolysiloxane; carrier gas: hydrogen (90 kPa); split injector (1:30), injection temperature: 280°C; FID detector, detection temperature: 250°C; temperature program: 170°C (isotherm); solvent: ethyl acetate; tR of the products: tR (2R,4'R,8'S) = 126.0 min, tR (2R,4'R,8'R) = 127.5 min, tR (2R,4'S,8'S) = 129.5 min, tR (2R,4'S,8'S) = 132.0 min; and tR (2S,4'S,8'R) = 126.0 min, tR (2S,4'S,,8'S) = 127.5 min, tR (2S,4'R,8'S = 129.5 min, tR (2S,4'R,8'R) = 132.0 min. 1H-NMR (400.1 MHz, CD2C12): 5 = 0.87 (d, 3J = 6.6 Hz, 3 H, *CH-C#3), 0.88 (d, 3J = 6.6 Hz, 3 H, *CH-C#3), 0.89 (d, 3J = 6.6 Hz, 6 H, CH(C#3)2), 1.03 - 1.65 (m, 21 H, 9 CH2, 3 CH), 1.29 (s, 3 H, 0-*C-CH3), 1.77 (m, 2 H, 0-*C-CH2), 2.09 (s, 3 H, Ph-CH3), 2.10 (s, 3 H, Ph-CH3), 2 ,72 (m, 2 H, CH2 (cycl), 3.74 (s, 3 H, -O-CH3), 6.43 (s, 1 H, ar. CH). Example 68 : (2R)-'γ-tocophenyl acetate (2R,3'E,7'E)-'γ~Tocotrienyl acetate (22.7mg, 0.05mmol), catalyst (5 x 1 0-7 mol, 1 mol%) and dichloromethane (0.5ml) were added under nitrogen to a 2ml glass vial containing a magnetic stir bar and placed in an autoclave. The autoclave was pressurized to 50 bar with H2 and the solution stirred at 700 rpm for 2 hours. The pressure was then carefully released and the reaction mixture concentrated under reduced pressure, Hexane (1 ml) was added and the mixture filtered through a 0.2um syringe filter. The hexane solution was then concentrated to give 23 mg (100%) of (2J?)-y-tocopheryl acetate (>98 % 2R,4'R,8'R; We Claim: 1. Process for the manufacture of at least one compound of the formula I wherein the position labelled with the asterisk is an asymmetry center and R' is selected from the group consisting of linear C~.~-alkylC, 5-7-cycloalkyl, hydroxyl, hydroxyalkyl (alkyl = CI4-alkyl), oxoalkyl (alkyl = CI4-alkyl), alkylcarbonyl (alkyl = C14-alkyl), alkoxycarbonyl (alkoxy = linear CI4-alkoxy) and a group of the formula with R* being a hydroxyl group or a protected hydroxyl group, and R~ and R4 being independently from each other hydrogen or methyl, and n being an integer from 1 to 10, preferably from 1 to 3, comprising the step of hydrogenating a compound of the formula II wherein at least one carbon-carbon double bond is present, and wherein the dotted lines represent the possible positions of such facultative carbon-carbon double bonds; and R' and n are as above, in the presence of a chiral lr complex as the catalyst wherein the lr complex is of the formula Ill, IV, V, VI, VII, VIII, IX, X, XI or XV, or the corresponding enantiomeric formula wherein R, XI, x2, x3, x4, x5, x6, x7, x8, x9, XI', XI', xI2, xI3, xI4, xq5, xI6, xq7, XI', xlglx 2O1x 2' and x~~a re independently from each other hydrogen, C14-alkyl, C5-7-cycloalkyl, phenyl which is optionally substituted with one to three CI4-alkyl, CI4-alkoxy and/or C14-perfluoroalkyl groups, benzyl, I -naphthyl, or ferrocenyl, the anion Y is a low coordinating anion, n is 1 or 2, and "o-To~'m~ eans ortho-tolyl, "Ph" means phenyl, "TBDMS" means tert-butyldimethylsilyl, "p-Tol" means para-tolyl, "BArFn means tetra(3,5- bis(trifluoromethyl)phenyl)borate, or the Ir complex is of the formula Ill, IV, V, VI, VII, VIII, IX, X, XI or XV, or the corresponding enantiomeric formula whereby the cyclooctadiene ligand is replaced by ethane or norbomadiene. 2. The process as claimed in claim 1, wherein one stereoisomer of compound I is produced in excess. 3. The process as claimed in claim 1 and/or 2, wherein the compound of the formula II is an isoprenoid, a non-cyclic sesquiterpene, a tocomonoenol, a tocodienol, a tocotrienol or any derivative thereof which is hydrogenated to the corresponding compound of the formula I, preferably to a highly stereoisomerically enriched corresponding compound of the formula I. 4. The process as claimed in claim 3, wherein the tocomonoenol, the tocodienol, the tocotrienol and/or any derivative thereof is of the formula XIII, wherein the dotted bonds are optional and at least one of the dotted bonds is present, and wherein R* is a hydroxyl group or a protected hydroxyl group and R3 and R4 are independently from each other hydrogen or methyl. 5. The process as claimed in one or more of the preceding claims, wherein the amount of the catalyst is from about 0.05 to about 5 mol %, preferably from about 0.09 to about 2.5 mol %, more preferably from about 0.1 to about 2.0 mob%, based on the amount of the compound of the formula II. 6. The process as claimed in one or more of the preceding claims, wherein the compound of the formula II is selected from the group consisting of (E)- geranylacetone, (E)nerylacetone, (Z)-nerylacetone, (E)-dihydrogeranylacetone, (E)-dihydronerylacetone, (Z)-dihydronerylacetone, (all-E)-farnesol, (2E,6E)- farnesene acid ethyl ester, (2Rl3'E,7'E)-a-tocotrienol, (2Rl3'E,7'E)-P-tocotrienol, (2RI3'E,7'E)-y-tocotrienol, (2RI3'E,7'E)-6-tocotrienol, derivatives and mixtures thereof, as well as any part or extract of a plant oil containing at least a tocotrienol or a derivative thereof. 7. Process as claimed in claim 1, wherein the compound of the formula II is (E)- nerylacetone or (Z)-nerylacetone or (E)-geranylacetone, which is hydrogenated to a mixture of the enantiomers (6s)-6,IO-dimethylundecane-2-one and (6R)-6,IOdimethylundecane- 2-one in the presence of a chiral Ir complex selected from the group consisting of catalyst A2, Dl, B1 and El, or their enantiomers wherein "0-Tol" means ortho-tolyl, "BArFn means tetra(3,5-bis(trifluoromethy1)- phenyl)borate, and "Ph" means phenyl, preferably in the presence of a chiral Ir complex selected from the group consisting of catalyst Dl, B1 and El or their enantiomers, more preferably in the presence of a chiral Ir complex selected from the group consisting of catalyst B1 and El or their enantiomers. 8. Process as claimed in claim 7, wherein one enantiomer is present in the mixture in an enantiomeric excess, preferably of at least 84%, more preferably of at least 90%. 9. Process as claimed in claim 1, wherein the compound of the formula I1 is (E)- farnesol, which is hydrogenated to a mixture of two enantiomeric pairs (3Rl7S)- 3,7,11 -trimethyldodecane-1-01 and (3SI7R)-3,7,1 1-trimethyldodecane-1-01 as well as (3RI7R)-3,7, 1 1-trimethyldodecane-1-01 and (3SI7S)-3,7,1 l-trimethyldodecane1- 01 in the presence of the chiral Ir complex El or B1 or the corresponding enantiomer, wherein "0-Toll1 means ortho-tolyl, "BArF1' means tetra(3,5- bis(trifluoromethyl)phenyl)-borate, and "Ph" means phenyl. 10. Process as claimed in claim 9, wherein the stereoisomer (3S17S)-3,7,11- trimethyldodecane-1-01 - compared to the other stereoisomers - is present in the mixture in excess, preferably in an amount of at least 70%, more preferably in an amount of at least 75%. 11. Process as claimed in claim 1, wherein the compound of the formula II is (E)- farnesene acid ethyl ester, which is hydrogenated to a mixture of two enantiomeric pairs (3R17S)-3,7,11-trimethyldodecanoic acid ethyl ester and (3S17R)-3,71, 1 - trimethyldodecanoic acid ethyl ester as well as (3R17R)-3,71, 1 - trimethyldodecanoic acid ethyl ester and (3S17S)-3,7,11- trimethyldodecanoic acid ethyl ester in the presence of the chiral Ir complex B1 or El or the corresponding enantiomer, wherein "0-Tol" means ortho-tolyl, "BArF1' means tetra(3,5-bis(trifluoromethyl)- phenyl)borate, and "Ph" means phenyl. 12. Process as claimed in claim 1 1, wherein the stereoisomer (3S17S)-3,71, 1 - trimethyldodecanoic acid ethyl ester - compared to the other stereo isomers - is present in the mixture in excess, preferably in an amount of at least 55%, more preferably in an amount of at least 70%. 13. Process as claimed in claim 1, wherein the compound of the formula II is (2R, 3'E,7'E)-a-tocotrienyl acetate, which is hydrogenated to a mixture of the four diastereoisomers (2R14'S,8'R)-a-tocopheryl acetate, (2R,4'S,8'S)-a-tocopheryl acetate, (2R,4'R,8'R)-a-tocopheryl acetate and (2R14'S,8'S)-a-tocopheryal cetate in the presence of the chiral Ir complex El, E2, E7, El5 or HI or the corresponding enantiomer, wherein one diastereoisomer is manufactured in excess, and "0-Tol" means o-tolyl, "Ph" means phenyl, "BArFY1 is tetra(3,5- bis(trifluoromethyl)-phenyl)borate, "n-Bu" means= n-butyl, and "Me" means methyl. 14. Process as claimed in claim 13, wherein, when the chiral Ir complex E2, El5 or HI is used as the catalyst, the stereoisomer (2Rl4'R,8'R)-a-tocopheryl acetate - compared to the other diastereoisomers - is present in the mixture in excess, preferably in an amount of at least 55%, more preferably in an amount of at least 90%. 15. Process as claimed in claim 1, wherein the compound of the formula II is (2s ,3'E,7'E)-a-tocotrienyl acetate, which is hydrogenated to a mixture of the four diastereoisomers (2S,4'S,8'R)-a-tocopheryl acetate, (2S,4'R,8'S)-a-tocopheryl acetate, (2S,4'R,8'R)-a-tocopheryl acetate and (2S,4'S,8'S)-a-tocopheryl acetate in the presence of a chiral Ir complex selected from the group consisting of E3, E4, E6, E8, E9, E10, El I , E12, E13, El4 or their enantiomers as the catalyst, wherein "Ph" means phenyl, "BArFn is tetra(3,5-bis(trifluoromethyl)phenyl)borate [B(3,5-C6H3(CF3)2)4]-",C yll means cyclohexyl, "Me" means methyl, and "n-Bu" means n-butyl, preferably in the presence of the chiral Ir complex El3 or El4 or the corresponding enantiomer as the catalyst, whereby one diastereoisomer is manufactured in excess. 16. Process as claimed in claim 1 5, wherein the diastereoisomer (2Sl4'S,8'S)-atocopheryl acetate is present in the mixture in excess - compared to the other diastereoisomers, preferably in an amount of at least 65%, more preferably in an amount of at least 85%. 17. Process as claimed in claim 1, wherein the compound of the formula II is (2Rl3'E,7'E)-y-tocotrienyl acetate which is hydrogenated to a mixture of the four diastereoisomers (2Rl4'S,8'R)-y-tocopheryl acetate, (2Rl4'R,8'S)-y-tocopheryl acetate, (2R,4'RI8'R)-y-tocopheryl acetate and (2Rl4'S,8'S)-y-tocopheryl acetate in the presence of the chiral Ir complex C1, Dl, El, F1 or HI whereby "Ph" means phenyl, "Bn" means benzyl, "BArf is tetra(3,5- bis(trifluoromethyl)-phenyl)borate[B(3,5 "o-Tol" means o-tolyl, and "TBDMS" means tert-butyl-dimethyl silyl, as the catalyst, whereby one diastereoisomer is manufactured in excess. 18. Process as claimed in claim 17, wherein, when the chiral Ir complex F1 or its enantiomer is used as the catalyst, the diastereoisomer (2RI4'R,8'R)-a-tocopheryl acetate is present in the mixture in excess - compared to the other diastereoisomers, preferably in an amount of at least 45%. 19. A process for the manufacture of a hydrogenated part or extract of a plant oil, preferably of palm oil, comprising the step of hydrogenating the part or extract of the plant oil comprising at least a tocotrienol or derivative thereof in the presence of a chiral Ir complex as the catalyst, wherein the chiral Ir complex is of one of the formulae Ill to XI and XV or the corresponding enantiomers wherein R, XI, x2, x3, x4, x5, x6, x7, x8, x9, x", XI', xI2, xI3, xI4, xI5, xI6, xI7, x ' ~ ,x I9, x20, x2' and x~~a re independently from each other hydrogen, C1-4-alkyl, C5-7-cycloalkyl, phenyl which is optionally substituted with one to three Ct4-alkyl, CI4-alkoxy and/or Cq4-perfluoroalkyl groups, benzyl, I-naphthyl, or ferrocenyl, the anion Y is a low coordinating anion, n is 1 or 2, and "0-Toll1 means ortho-tolyl, "Ph" means phenyl, "TBDMS" means tert-butyldimethylsilyl, "p-Tol" means para-tolyl, "BAr? means tetra(3,5- bis(trifluoromethyl)phenyl)borate, or the Ir complex is of the formula Ill, IV, V, VI, VII, VIII, IX, X, XI or XV, or the corresponding enantiomeric formula whereby the cyclooctadiene ligand is replaced by ethane or norbomadiene. 20. The process as claimed in claim 19, wherein the tocotrienol or the derivative thereof is hydrogenated to a tocopherol and the derivative thereof, respectively, preferably to highly stereoisomerically enriched (all-R)-tocopherol (derivative).

Documents:

5205-delnp-2007-abstract.pdf

5205-delnp-2007-Claims-(03-12-2013).pdf

5205-delnp-2007-claims.pdf

5205-delnp-2007-Correspondence Others-(03-12-2013).pdf

5205-delnp-2007-Correspondence Others-(31-05-2013).pdf

5205-delnp-2007-correspondence-others.pdf

5205-delnp-2007-description (complete).pdf

5205-delnp-2007-drawings.pdf

5205-delnp-2007-form-1.pdf

5205-delnp-2007-form-2.pdf

5205-delnp-2007-Form-3-(03-12-2013).pdf

5205-delnp-2007-form-3.pdf

5205-delnp-2007-form-5.pdf

5205-delnp-2007-gpa.pdf

5205-delnp-2007-pct-210.pdf

5205-delnp-2007-pct-304.pdf