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United States Patent (19 11 3,978,147 Wilke Et Al

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United States Patent (19 11 3,978,147 Wilke Et Al United States Patent (19 11 3,978,147 Wilke et al. (45) Aug. 31, 1976 (54) PROCESS FOR THE PREPARATION OF Klaus Naumann et al., J. Amer. Chem. Soc., 91:25 OPTICALLY ACTIVE CARBON Dec. 3, 1969, pp. 7012-7023. COMPOUNDS W. R. Moser, J. Amer. Chem. Soc. 91:15, 1969, pp. 75 inventors: Ginther Wilke; Borislav 1 137-1 38. Bogdanovic; Horst Pauling, all of Mulheim (Ruhr), Germany Primary Examiner-Delbert E. Gantz Assistant Examiner-C. E. Spresser 73) Assignee: Studiengesellschaft Kohlem.b.H., Attorney, Agent, or Firm-Burgess, Dinklage & Mulheim (Ruhr), Germany Sprung 22 Filed: Nov. 7, 1973 21 Appl. No.: 413,722 57 ABSTRACT Related U.S. Application Data Optically active compounds are prepared from opti cally inactive unsaturated hydrocarbons by reacting at 63) Continuation-in-part of Ser. No. 166,957, July 28, least one unsaturated hydrocarbon in the presence of 1971, abandoned. a catalyst prepared by combining a nickel compound, 30 Foreign Application Priority Data a Lewis acid and an optically active phosphine of the Aug. 6, 1970 Germany............................ 2039 125 general formula 52 U.S. C. ........................ 260/666 A; 260/666 B; PR'R'R'' 260/666 PY (51 Int. Cl.’............................................ C07C3/00 in which R', R'' and R'' are hydrocarbon radicals, 58 Field of Search................ 260/666 AB, 666 PY thereby forming optically active compounds having chiral centers formed by the carbon-to-carbon link 56 References Cited ages. The optically active compounds can be polymer UNITED STATES PATENTS ized to provide optically active polymers. 3,271,468 9/1966 Wilke et al......................... 260/668 8 Claims, No Drawings OTHER PUBLICATIONS Klaus Naumann et al., J. Amer. Chem. Soc., 91:10, May 7, 1969, pp. 2788-2789. 3,978,147 1. 2 acid and an optically active phosphine of the general PROCESS FOR THE PREPARATION OF formula PR'R'R' in which R', R'' and R'' are hydro OPTICALLY ACTIVE CARBON COMPOUNDS carbon radicals. RELATED APPLICATION DESCRIPTION This application is a continuation-in-part application The catalysts known from the literature, as described of copending application Ser. No. 166,957 filed July above, are unable to combine two different unsaturated 28, 1971, now abandoned. hydrocarbons to develop optically active centers. The optically inactive starting compounds suitable BACKGROUND 10 for the synthesis are unsaturaed hydrocarbons, such as This invention relates to a process for the preparation open-chain, or cyclic olefins containing at least one of optically active carbon compounds. double bond, wherein chiral centers can be formed by The process relates to the preparation of optically the carbon-to-carbon linkages. active carbon compounds from optically inactive hy The catalysts are prepared from various compounds drocarbons, with development of the chiral centers by 15 of nickel, such as at-allyl-Ni-X of the general formula the carbon-to-carbon linkages. Chemical literature reveals only three examples of non-enzymatic, asymmetrical catalysis by way of C-C R2 Ra linkage. J. Furukawa et al. (Bulletin of the Chemical --. Soc. of Japan, Vol. 41, 155 (1968) describe the synthe 20 sis of optically active trimethyl cyclododecatrienes in which X is a chlorine, bromine or iodine atom, R to from pentadi-1,3-ene, using a catalyst of titanium tetra Rs are alkyl, aralkyl or aryl radicals or hydrogen atoms menthozyl and diethyl aluminium monochloride at and any two radicals can be linked together to form a 40°C. However, insufficient information is given re ring, or nickel -I-compounds, such as nickel hydrox garding the yield of the optically active products and 25 ide, nickel sulphide, nickel chloride, nickel cyanide, their optical purity and according to the indicated data, nickel bromide, nickel iodide, nickel carbonate, nickel the yields are not higher than 10% and 4%, respec formate, nickel acetate, nickel oxalate, nickel benzo tively. The authors themselves point out that the opti ate, nickel acetylacetonate, nickel acetoacetate ester, cal purities cannot be high, since the rotations are nickel benzoyl acetonate, nickel dimethylglyoxime, small. 30 nickel oxide or nickel tetracarbonyl or even nickel H. Nozaki et al. (Tetrahedron Vol. 24, 3655 (1968) (O)-compounds, such as nickel tetraphenyl isonitrile, obtained trans-1-methyl-2-phenylcyclopropane from nickel tetra-p-bromophenyl isonitrile, nickel monocar diazomethane and 1-methyl-2-phenyl-ethylene with a bonyl-trimethyl isonitrile or nickel-bis-acrolein, nickel yield of optical product of less than 8% at 60°C, with bis-acrylonitrile, nickel-bis-acrylonitrile dipyridyl, the aid of a catalyst consisting of an optically active 35 nickel-bis-fumaronitrile, nickel-bis-cinnamic acid ni cupric complex. Cuprous chloride catalysts with com trile or bis-at-allyl nickel, bis-cyclooctadiene nickel. plex-bonded trialkyl or triaryl phosphite ligands were The Lewis acids which may be particularly used are used by W. R. Moser (J. Amer. Soc. 91:15, 1135 (1969) aluminium alkyls, aluminium alkyl halides or alumin for the synthesis of optically active cyclopropane deriv ium halides, such as aluminium trialkyls, dialkyl alu atives from ethylene diazocetate and styrene. The ( 40 minium hydrides, dialkyl aluminium halides, alkyl alu (-)-tribornyl-phosphite)-cuprous chloride produced minium sesquihalides, alkyl aluminium dihalides, dial the corresponding cyclopropane, derivatives with an kyl aluminium alkoxyls. It should be noted that if nick optical yield of about 3% at 30 to 60°C. el-II-compounds are used, the Lewis acids must contain The optical purities of the compounds produced by reducing groups. the above methods are unsatisfactory, because, firstly, 45 Phosphines (PR'R'R'') are the ligands used to in the inducing groups on the catalyst are exchanged dur duce the optical activity according to the invention. ing the reaction for inactive groups and, secondly, the The radicals R', R'' and R'' are hydrocarbon radi reactions mentioned in the examples only proceed at cals preferably containing from 1 to 30 carbon atoms. relatively high temperatures. Suitable hydrocarbon radicals include saturated, unsat 50 urated, parafinic, naphthenic, olefinic, acetylenic and SUMMARY aromatic hydrocarbons. It has now been found that optically active carbon The phosphines either contain the phosphorus atom compounds can be prepared from optically inactive as a chiral center, in which case R'R'R' represents hydrocarbons with C-C linkage and have optical puri three different radicals which are bonded to the phos ties which hitherto could not be produced by any cata 55 phorus and one of the enantiomers (*PR'R'R'') has lytic process. , been obtained by racemate cleavage, or in which opti The invention therefore provides a process for the cally active radicals R* are bonded to the phosphorus preparation of optically active carbon compounds from atom (PRR). The combination of both types is also optically inactive unsaturated hydrocarbons which possible, so that phosphines with chiral phosphorus and comprises reacting at least one unsaturated hydrocar 60 optically active radicals, e.g. (*PR'R'R''*) can be bon in the presence of a catalyst prepared by combin used. ing at least one nickel compound, at least one Lewis Characteristic examples for the said three types are: shis 1. Phenyl-methyl-propyl-phosphine *P H H 3,978,147 ar 2. Tri-myrtanyl-phosphine ()-- 3 Menthyl-dimethylphosphine v Dimenthyl-methylphosphine P(CH), PCH pH-in-chi-ch.sk 3. Menthyl-amyl-i-propylphosphine - ** PP'N, CH The phosphines of the second type can be prepared ric functional groups have been introduced into insolu particularly easily but nevertheless highly active, since ble polymers for this purpose. Alternatively, optically it is possible to make use of optically active natural active components were condensed to yield insoluble products, without having to carry out the racemate resins to resolve enantiomers in this way. cleavage operations. The best results obtained by the Chromatography on a column filled with poly((S)-3- process of the invention are when the radicals R of the 35 methyl-1-pentene) results in the separation of po phosphines have a considerable steric bulk. ly((R)-(S)-4-methyl-1-hexene) or poly((R)(S)-3-meth The process of the invention can be carried out yl-1-pentene) into levorotatory and dextrorotatory within a wide temperature range, namely between ap fractions. Optically inactive crystalline poly(propylene proximately -120° and +100°C. The preferred reaction oxide) may be separated into optically active fractions. temperatures are between -78 and 0°C. 40 In these cases one is not dealing, strictly speaking, with The reacton can take place at atmospheric pressure, a separation of antipodes. or above atmospheic pressure and the reaction pres Optically active polymers such as soluble or cross sure is determined at the reaction temperature by the linked poly((S)-isobutylethylenimine) have been used vapour pressure of the olefines and of the solvent being as a catalyst for an asymmetric cyanohydrin synthesis, used. 45 the optical yield being as high as 20%. The principle of The process can be carried out in an inert solvent, for using optically active polymers as asymmetric catalysts example, chlorinated hydrocarbons, such as chloroben should be applicable to other syntheses as well. All zene or methyl chloride. It is recommended that care enzymatic reactions and matrix-directed biosyntheses fully purified and anhydrous solvents should be used. probably operate in this way. Autocatalysis in the prep By means of the process according to the invention, 50 aration of optically active polymers is known. it becomes possible to prepare optically active hydro An isotatic macromolecule can be synthesized by carbons by a catalytic procedure, which hydrocarbons polymerizing (-)-propylene oxide with potassium hy contain functional groups in addition to the chiral car droxide (JACS 78, 4787 (1958)). The feature of bon atoms, so that further conversions are possible, for steroregularity is built into the monomer because all example, the polymerization of optically active vinyl 55 the monomer units have the same configuration as the cyclooctene or 3-methyl-pentene-1 (cf.
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