CA1109074A - Asymmetrical hydrogenation and related means for this purpose - Google Patents

Asymmetrical hydrogenation and related means for this purpose

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Publication number
CA1109074A
CA1109074A CA275,775A CA275775A CA1109074A CA 1109074 A CA1109074 A CA 1109074A CA 275775 A CA275775 A CA 275775A CA 1109074 A CA1109074 A CA 1109074A
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aryl
reaction
carried out
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alkyl
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French (fr)
Inventor
Mario Fiorini
Matteo Giongo
Francesco Marcati
Walter Marconi
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SnamProgetti SpA
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Priority claimed from IT2265376A external-priority patent/IT1063212B/en
Priority claimed from IT2013977A external-priority patent/IT1113753B/en
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Priority to CA000374038A priority Critical patent/CA1119183A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/60—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0073—Rhodium compounds
    • C07F15/008—Rhodium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
    • C07F9/4883—Amides or esteramides thereof, e.g. RP(NR'2)2 or RP(XR')(NR''2) (X = O, S)

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

ABSTRACT OF THE DISCLOSURE:
The invention relates to the asymmetrical hydro-genation of compounds selected amongst prochiral and racemic olefins and compounds containing CO and/or CN
groups. For this hydrogenation use is made of catalytic complexes of optically active compounds of the aminophosphine class and of transition metals. The invention relates moreover to the preparation of these complexes.

Description

~9074 The present invention relates to optically active compounds belonging to the class of the aminophosphines, and to their use, together with suitable derivatives of transition metals, in the asymmetrical hydrogenation of a broad range of compounds, selected amongst prochiral and racemic olefins and the compounds containing CO and/or CN groups.
The preparation on industrial basis of optically active organic compounds having high optical purity, such as for instance levorotatory amino acids, is still now almost exclu-sively depending on processes of biochemical or microbiologicaltype.
Until some years ago no approaches of pure chemical nature were known which, due to the process economy and to the optical yield, were able to compete with the above mentioned methods.
However, the discovery of new homogeneous catalytic systems having high stereospecificity, such as for example tris (triphenyl-phosphine) chloro-rhodium, and the new developments in the synthesis of asymmetrical phosphorus based phosphines lead to the preparation of chiral complexes of transition metals having high stereoselectivity in the hydrogenation of prochiral olefins.
We found now a process permitting the preparation of a wide range of active complexes for the asymmetrical hydrogen-ation of unsaturated compounds, more particularly of olefins, with high conversion and optical purity.
In fact, the object of the present invention is a complex of a transition metal with an asymmetrical aminophosphine of the general formula:
P Rx (NR R )3 x wherein Rl is alkyl, aryl, alkylaryl, cycloalkyl, alcoxy,aryl-oxy, alkylthio, arylthio , alkylphosphino , arylphosphino or aminophosphino; x varies between 0 and 2;R2 and R3 are identical f~ -- 2 `~i ~19~1~4 or different an~ each represents an alkyl, aryl,alkylaryl,aryl-alky],cycloalkyl radical, at least one of the radicals R2 and R containing one or more non racemic chiral centers.
The radical NR2R3 represents optically active ~uno groups deriving from the amino compounds as hereinafter described, which consti-tute a wide category of mono- and poly-~entate ligands~ capable of coordinating transition metals, thus forming complexes sui~-able for the asymme-trical hydrogenation, with high conversion level~ of prochiral and racemic olefins~ to produce the corre-sponding satura-ted compounds with a good opbica] purity. The reparation ol the amino-pllosl)llo-org.lnic coml)owlds is carried out starting from compounds having the formula 1~2 _ _ n wherein~ when n is 1~ X may represent hydrogen~ an alkali metal or PR X; when n is 2~ X is a radical of the type -PR, R being selec~ed amongst the above mentioned radicals and, when n is 3, X represents P~ R and R3, identical or different from each other~ may represent an alkyl~ alkylaryl, aryl-a:lkyl~ cycloalkyl olle radical~ at least/of the two radicals containing one or more non racemic chiral centers. The said prep~ra~ion of the compounds can be carried Ollt according to one o~ tlle following schemes :
1 ) R~NH + R2PCl + B ~_ R -NH-PR2 + . HCl
2 ) RR Nll + R2PCl + B --~RR N-l'R2 +- IICl
3 ) RR NNa + R2PCl -~D RR N - PR2 + NaCl
4) 2RR NH + RPC12 +2B _ (RR N)2PR + 2 B HCl
5) R NH2 + 2 R2PCl + 2 ~R N(PR2)2 + 2 B- IICl
6 ) (RRl~N)2PR + ROII ~ (RR N)PR(OR) + I~NII
7 ) 3 RR Nll + I'C13 + 3 13 --b- ( 1~ N ) 3P + 3 IS IlCl wherein the groups R have the above meanings, B is an organic base~ or the preparation can ~e carried out accordin~ to already . ~

~5~7~

known processes and related to the corresponding achiral compounds.
Amongst the optically active amines (R*~H2) there can be for instance cited alpha-methyl-benzylamine, bornylamine, sec~-butylamine, menthylamine or any primary amine containing one or more non racemic chiral centers; or secondary amines (R RNH) wherein one or both the groups attached to the nitrogen atom contain one or more non racemic chiral centers. For ex-ample, unsubstituted N alpha-methylbenzylamine, pipecoline, desoxyephedrine, 0-substituted ephedrine, N-monosubstituted and N,N'-disubstituted ethylendiamine with at least a non racemic chiral substituent, piperazines containing one or more non race-mic chiral centers.
The ac1:ive catalytic complex is formed in the asymme-trical hydrogenation by reacting one of the above described ligands with a coordination compound of a metal of the transition series, preferably Cr Mo W Fe Co Ni Ru Rh Pd Pt Os Ir Cu Ag Au Ti V.
The ligands of the coordination compounds can be anionic or neutral. Amongst the anionic ligands the halogens, the cya-nide, nitrate, acetate, acetylacetonate, the sulfide and like ions can be cited. Amongst the neutral ligands, water, ammonia, amines, phosphines, carbon monoxide, olefins, diolefins and the like can be cited.
Amongst the representative compounds rhodium (III) hydra-ted chloride, ruthenium(III? chloride~ dichloro-tetrakis (tri-phenylphosphine)ruthenium( ), rhodium (I) ~-dichloro-tetrakis (ethylene)~ rhodium (I) Ju-dichloro-bis(norbornadiene), dichloro-tetraamino-platinum (II),dibromo-tetrakis(triphenylphosphine) pal-ladium can be indicated.
The molar ratio between the ligand and the complex of the transition metal, as expressed as the ratio between the number of 4.

110907,4 phosphorus atoms of the ligand and the number of metal atoms of the complex may vary between 1 and 15, the values of 2, 3, 4 being preferred.
The reaction solvents can be aromatic aliphatic hydro-carbons~ alcohols, ethers, ketones~ esters~ amides and their mixtures The reaction of asymmetrical hydrogenation is carried out at a molar ratio between the substrate and the catalyst variable between 10,000 and 10. The reaction temperature can be of between -70C and +200Co~ preferably of between O and 50C.
The hydrogen pressure is in the range of l and 100 atmospheres.
The following examples are illustrative of the characte-ristics of the invention, but should not anyhow be construed as a limitation EXAMPLE
N~N'-bis(S(-)alphamethylbenzyl)ethylendiamine is separa-ted starting from S(-)alphamethylbenzylamine and diethyl oxalate;
the reduction of the diamide is carried out with lithium aluminum hydride in THF and the corresponding diamine is isolated as the dihydrochloride, having melting point of 250C (yield : 80~).
After the dihydrochloride has been cleared by 10% NaOH, 0.050 moles of the diamine are treated with 0.100 moles of di-phenylchlorophosphine in 300 mls of anhydrous benzene, in the pre-sence of 0.200 moles of triethylamine.
The mixture is refluxed for 20 hours, the hydrochloride of triethylammoniùm being then filtered and the benzene solution is concentrated until N-N' bis (S(-)alpha-methylbenzyl) N-N' bis (diphenylphosphino) ethylendiamine is separated~ mOpO 138-140C
(yields of 70% with respect to the starting diamine).
3 / ~ 725 = _ 91.5 ( c = 1~ CHC13) The catalyst is prepared by treating 505mg of rhodium( ) Judichloro tetrakis(ethylene) (17.7 x 10-6 moles) with 22.5 mg of ilO9074 N~N' bis(S(-)alpha-methylbenzyl) N-N' (diphenylphosphino) ethylendiamine (35.4 x 10-6 moles)~ 6 mls of anhydrous benzene being used as the solvent.
Atomic ratio P/Rh ~ 2 The solution is -transferred into a flask containing 2.8 g of alpha-acetamido cinnamic acid in 24 mls of anhydrous methanolg the flask being connected to an hydrogenating appara-tus operating at atmospheric pressure and thermostated at 25C, by which a careful purge with hydrogen of the reaction environ-ment is affected before the catalytic complex is addedO
The reaction pattern is monitored through the normal gauging techniques.
The initial rate of hydrogen absorption is of about 4 mls/min., as measured under the operating conditions.
After 3 hours the conversion is about 85%. The reaction is terminated and the reaction product is separated by evaporating the solvent under reduced pressure .
The residue product is treated by a 0.5 N NaOH solution and the insoluble catalyst is filtered.
The aqueous solution is made acidic to pH 2-3 with dilu-ted HCl~ and the organic phase is extracted five times with ethyl ether; the combined ethereal fractions are dried over Na2SO40 The ether is then evaporated. The residue product, examined by N-spectroscopic route (NMR, IR) consists of R(-)acetylphenyl ala-nine / d 7 = -40 ( c = 1~ EtOH 95%) with an optical yield of 84%; the specific rotation for enantiomeric pure S(+) N-acetyl phenyl alanine is / ~ 7 = + 4705 ( c = 1~ EtOH 95%)0 By repeating the process described in the Example 1 and by using R(+) alpha methylbenzylamine, the N-N'(R(+)alphamethyl benzyl) N-NI (diphenylphosphino) ethylendiamine is prepared~
having the two centers of chirality of opposite configuration 11()9074 with r-espect to -those of the diphosphine of the Example 1.
The ligand is reacted with the complex of rhodium(I) and the catalytic complex is used in the hydrogenation of alpha-acetaminocinnamic acid. The hydrogenated product~ after isolation and examination as in the Example 1~ consists of S(+) N-acetyl phenyl alanine~ having an observed rotation / CC 7 = + 38 9 (c = 1~ EtOH 95%) indicating an enantiomeric purity of 82%.
EXAMPLE~ A3 2(S)~5(S) dimethylp.iperazine is prepared through the cyclodimerization or S(-) alanine and reduction of the resulting diketopiperazine by l.ithium aluminium hydride ~
Th.e subsequent reaction of the above mentioned piperazine with diphenyl ch.lorophosphine in the presence of triethylamine leads to the formation of 2(S),5(S) dimethyl N,N' diphenylphos-phino (+) piperazine / ~_7 3 = + 78 ( c = 1~ THF). Yield 60%.
By operating according to the Example l~ the thus prepa-red ligand (134 x 10-6 moles) is reacted with rhodium (I))udichloro tetrakis ethylene (67 x 10-6 moles) and this catalytic complex is used in the hydrogenation of alpha-acetamidocinnamic acid (13 x 10 3 moles) at 25C and under atmospheric pressure. ~ .:
N acetyl (S) phenyl alanine is thus obtained with a yield of 80-85%~ / 0~ 7 = + 0.5 ( c = 1~ EtOH 95%). Optical purity : 1%.
~ D

The catalytic complex prepared according the technique of the Example 1~ starting from 4709 mg of rhodium(I)~udichloro tetrakis cyclooctene (66.8 x 10-6 moles) and 86 mg of N-N' (S(-) methylbenzyl) N-N' (diphenylphosphino) ethylen-diamine (135 x 10-6 moles) is used in the catalytic hydrogenation of 3-acetoxy 4-methoxy alpha-acetamido cinnamic acid ( 2 g) under atmospheric pressure at 25Co By operating as described in the Example 1, 3-acetoxy 4-methoxy N acetyl (R) phenylalanine is isolated from the reas~tion medium with a yield of 85-90%~ / d 7 = -16.9 c = 1, acetone).
The optical yield is 77%, and the enantiomeric pure 3-acetoxy 4-methoxy N-acetyl (R) phenyl alanine has / o~ 7 - 22 ( c = 1, acetone).
EXAI~IPLE 5 l-phenyl,295 S(-)alpha-methylbenzyl, l-phospha-2,5-azacyclopentane ls prepared by reacting N~N'-(S(-)-alphamethyl-benzyl) ethylendiamine with phenyl-dichlorophosphine in the pre-sence of triethylamine 380 x 10 moles of the compound are reacted with 95 x 10 6 moles of rhodium (I))udichloro tetrakis (ethylene) ( P/Rh = 2)o By opera-ting according to the Example 3 the catalyst is used in the hydrogenation of acetamino acrylic acid~ under 15 atmospheres of hydrogen and at room temperature.
The enantiomeric pure N-acetyl S(-) alanine is obtained with a yield of 85-90% and has / a~ 7D5 = ~ 5 ( c = l~ H20).
Optical yield 7.5 The enantiomeric pure N-acetyl R(-) alanine has / 0~ 7 5 ~
= 66.5 ( c = 2, H20). D

The catalytic complex prepared according to the Example l~ starting from rhodium( )Judichloro tetrakis (ethylene) (73 x 10 moles) and N,N' (S(-)alpha-methylbenzyl) N~N' (diphenyl-phosphine) ethylendiamine (146 x 10-6 moles) is used in the cata-lytic hydrogenation of 3.4 methylendioxy) alpha-acetamido cinnamic acid (6.98 x 10 3 moles) at 25C and under atmospheric pressure.
By operating as described in the Example 1~ 3~4 methylen-dioxy, N acetyl (R) phenyl alanine is isolated with quantitative yield~ 7 = - 40 ( c = 1.8, EtOH 95%). Optical yield: 75%.
~ D
The enantiomeric pure 3-4 methylendioxyg N acetyl (R) phenylalanine has / ~ 7 = - 5304 ( c = 1.8, EtOH 95%).

1109~74 The catalytic complex as prepared according to the techniq-ue of the Example 1, starting from rhodium(I) ~dichloro-tetrakis (cyclooctene) (13~g x 10-6 moles) and N~NI~S(-)alpha-methylbenzyl) N~N' (diphenyl-phosphino) ethylendiamine (27.5 x 10 6 moles) is uscd in the catalytic hydrogenation at 25C and under atmospheric pressure o-E alpha-acetamido acrylic acid (15.5 x 10 3 moles)~
The N acetyl (R) alanine which is isolated with quanti-10 tative yïeld has / ~ 7 5 = 48.5. Optical yield : 73%.

The catalytic complex prepared as described in the Example 1~ starting from rhodium ( ) ~dichloro tetrakis (cyclo-octene) (146 x 10 6 moles) and N~N'(S(-)alpha-methylbenzyl) N~
N' (diphenylphosphino) ethylendiamine ( 278 x lo moles)~ is used in the catalytic hydrogenation of the methyl ester of alpha-acetamido cinnamiG acid ( 13.7 x lo 3 moles). The R(-) N acetyl-phenyl alanine methyl ester~ which is isolated by chromatography on silica gel~ has / o~ 7 5 = - lo (c = 1.9g MeOH).
Optical yield : 46 o5% .
The enantiomeric pure S(-) N acetyl phenylalanine methyl ester has / 0~ 725 = ~ 21.4 ( c = 1.9, MeOH).

The catalytic complex as prepared according to the tech-nique described in the Example 1~ starting from rhodium (I) ~dichloro-tetrakis (ethylene) (77 x lo moles) and N~N' (S(-) alpha-methyl-benzyl) N9N' (diphenylphosphino) ethylendiamine (154 x 10-6 moles), is used in the catalytic hydrogenation of propan-2,3-dicarboxylic acid (15 X lo 3 moles) at 15,5 atmospheres and 30c~
The propan 2~3 dicarboxylic (R) acid~ isolated with quanti-tative yield, has / o~ 7 5 = - 1.5 ( c = lg H20). Optical yield :10%.

116~g~'74 The ~atalytic complex as prepared according to the technique described in the Example 1~ starting from rhodium( ) ~d:ichlo:ro tetrakis (ethylene) ( ~2 x 10 6 moles) and N~N~(S(-) alpha-methylben~yl NgNI (diphenylphosphino) ethylendiamine (146 x 10 moles)9 is used in the catalytic hydrogenation of alpha-methyl cinnamic acid at 5 atmO a~d 25~C. The 2-benzyl propion.ic (S) acid~ as quantitatively recovered according to the disclosure of the Example 1, has / ~ 7 5 = - 1 ( c ~ l,benzene).
Optical y:ie].d : 4%q D
EXAMPLE 1].
. . . _ 7 mls of anhydrous methanol and 5 g of acetophenone are charged .in an autoclave under nitrogen atmosphere; a solution of 2 mls of ber-zene containing 1807 mg of rhodiumchl.oro-norbornadiene ~RhClNBD 7 dimer and 5603 mg of N-N' bis (S(-)alpha-methylbenzyl)--N-N' (diphenyl.phosphino) ethylendiamine (PNNP) is then added.
After establishing a vacuum condition~ the autoclave i.s charged wi-th 112 at the pressure of 12 atmospheres. After 12 hours at room temperature 4 atmospheres of hydrogen were absorbed with a conversion of about 80%o The reaction is stopped at this time;
benzene and methanol are removed under reduced pressure and then, by fractionated vacuum distillation, 3.9 g of a product are re-co~ered whichS after analysis by spectroscopic route ~MR), con-sists of R(~)l-methyl-phenyl-carbinol / ~ 7D = ~7-4 (pure product). Optical purity : 17% ( / ~ 7 = ~ 44.2).

The catalyst is prepared from 45 mg of /RhClNBD 72 and 124 mg of (PN~P) in 3 mls of benzeneO Such a catalytic solution is charged in an autoclave containing 5 g of cycl.ohexyl-methyl-lc~o~o -in 7 mls of methanol. The autoclave is brought to 12 atmosphere pressure with hydrogen. After 48 hours at room temperature about 3 atmO of H were absorbed; the reaction is terminated; with a process like that of Example 1~ 3015 g of a 10~

11(~9~74 product are recovered~ which is R (-) l-cyclohexyl-ethanol 72 = _ 0 430 (pure compound) with optical yield of 8~.
~ D
( /-OC 7 20 5 5) D
EXA~IPLI 13 A flask containing 2 mls of benzene is charged with 24.2 mg of /RhClNBD 72 and 66.8 mg of (PNNP), thereafter add-ing 2.28 mls of diphenylsilane. The flask is cooled at 0C

and 1.21 g of acetophenone-anil (0- N = C - 0) in 6 mls of ben-zene are added dropwise . After 12 hours, still at 0C, 4 mls of 10% HCl and acetone are added until a homogeneous solution is obtained~ after filtration of the hydrolysis products~ After removal of the acetone under reduced pressure~ 100 mls of 5%
HCl are added and the mixture is extracted six times with 25 mls of Et20. The aqueous phase is made alkaline with 2N NaOH, and the new organic phase~ as obtained by extracting four times with 20 mls of Et20, is dried over Na2S04; then the ether is removed.
The residue product is distilled under vacuum 700 mg being obtain-ed, at the end, of a compound identified as R(-)N-phenyl-N-methylbenzylamine, having / ~ 7 = - 3.29 ( c = 2.15~ EtOH).
Optical purity : 12.2% ( /~ 720 = 26.1).

By operating as described in the Example 3 and by using a catalytic solution comprising 19 mg of j~hClNBD ~ and 55 mg of (PNNP) in 2 mls of benzene~ 4.3 g of ethyl piruvate in 10 mls of benzene are reacted with 5.79 g of Diphenyl silane in 5 mls of benzeneO In this Example3 differently from the Example 3, the silane is added dropwise to the solution of the other reactants maintained at 0C. After 2 hours, still at 0C, the hydrolysis is effected by means of 30 mls of MeOH containing 10 mg of p-toluen-sulphonic acid~ After filtration and removal of the methanol, llV9~74 3.5 g of D(~) ethyl lactate, / ~ 7 = + 3.25, arc isolatedby fractionated distillation, Optical purity : 22.4% (/ o~7 = 14~5)~

Claims (9)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A complex of a transition metal with an asymmetrical aminophosphine of the general formula:

P R? (NR2R2)3-x wherein R1 is alkyl, aryl, alkylaryl, cycloalkyl, alcoxy, aryl-oxy, alkylthio, arylthio, alkylphosphino, arylphosphino or aminophosphino; x varies between 0 and 2; R2 and R3 are identical or different and each represents an alkyl, aryl, alkylaryl, aryl-alkyl, cycloalkyl radical, at least one of the radicals R2 and R3 containing one or more non racemic chiral centers.
2. A process for the preparation of a complex as defined in claim 1, which comprises reacting an asymmetrical aminophosphine having the general formula:
P R? (NR2R3)3-x wherein R1 is alkyl, aryl, alkylaryl, cycloalkyl, alcoxy, aryl-oxy, alkylthio, arylthio, alkylphosphino, arylphosphino or aminophosphino; x varies between 0 and 2; R2 and R3 are identical or different and each represents an alkyl, aryl, alkylaryl, arylalkyl or cycloalkyl radical, at least one of the radicals R2 and R3 containing one or more non racemic chiral centers, with a coordination compound of a transition metal.
3. A process according to the claim 2, wherein the reaction is carried out at a molar ratio between the amino-phosphine and the coordination compound of the transition metal, as expressed as the ratio between the phosphorus atoms and the transition metal atoms, of between 1 and 15.
4. A process according to the claims 2 or 3, wherein the reaction is carried out in the presence of a solvent selected from the group consisting of aromatic and aliphatic hydrocarbons, alcohols, ethers, ketones, esters, amides, and their mixtures.
5. A process for the asymmetrical hydrogenation of a substrate selected from the group consisting of prochiral and racemic olefins and compounds containing CO or CN groups, which comprises contacting the substrate with a complex as defined in claim 1, in a hydrogen atmosphere.
6. A process according to claim 5, wherein the reaction is carried out at a molar ratio between the substrate and the complex, of between 10,000 and 10.
7. A process according to claim 5, wherein the reaction is carried out at a temperature between -70°C and +200°C.
8. A process according to claim 7, wherein the reaction is carried out at a temperature between 0 and 50°C.
9. A process according to claim 5, wherein the reaction is carried out at a hydrogen pressure ranging from 1 to 100 atmospheres.
CA275,775A 1976-04-26 1977-04-06 Asymmetrical hydrogenation and related means for this purpose Expired CA1109074A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CA000374038A CA1119183A (en) 1976-04-26 1981-03-27 Asymmetrical aminophosphines, belonging to a novel class of amine derivatives of the phosphorus

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
IT22653A/76 1976-04-26
IT2265376A IT1063212B (en) 1976-04-26 1976-04-26 Asymmetric hydrogenation of olefins, carbonyl cpds. or nitriles - using transition metal complex of asymmetric amino-phosphine
IT20139A/77 1977-02-10
IT2013977A IT1113753B (en) 1977-02-10 1977-02-10 Asymmetric hydrogenation of olefins, carbonyl cpds. or nitriles - using transition metal complex of asymmetric amino-phosphine

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CA1109074A true CA1109074A (en) 1981-09-15

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IT1087963B (en) * 1977-10-17 1985-06-04 Snam Progetti ASYMMETRICAL HYDROGENATION OF PROCHIRAL OLEFINS BY COMPLEX OF TRANSITION METALS IMMOBILIZED IN CLAY MINERALS.

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FR2116905A5 (en) * 1970-12-10 1972-07-21 Inst Francais Du Petrole NEW BIDENT COORDINATES, THEIR MANUFACTURING AND THEIR APPLICATIONS

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CH629166A5 (en) 1982-04-15
DE2718533C3 (en) 1980-08-28
DE2759683B1 (en) 1980-07-17
JPS633871B2 (en) 1988-01-26
SE460066B (en) 1989-09-04
SE434918B (en) 1984-08-27
NL180096B (en) 1986-08-01
JPS52151127A (en) 1977-12-15
DE2718533A1 (en) 1977-11-24
SE7704738L (en) 1977-10-27
AU572169B2 (en) 1988-05-05
DD137233A5 (en) 1979-08-22
LU77197A1 (en) 1977-08-17
FR2349555A1 (en) 1977-11-25
DE2759684C2 (en) 1986-05-28
HUT34037A (en) 1985-01-28
NO771419L (en) 1977-10-27
FR2349555B1 (en) 1980-12-26
SE8304837L (en) 1983-09-09
DK180877A (en) 1977-10-27
AU3054684A (en) 1984-12-20
NL180096C (en) 1987-01-02
DE2718533B2 (en) 1979-12-20
GB1580461A (en) 1980-12-03
DE2759683C3 (en) 1981-10-15
DD132487A5 (en) 1978-10-04
HUT33991A (en) 1985-01-28
SE8304837D0 (en) 1983-09-09
YU107577A (en) 1983-02-28
NO773738L (en) 1977-10-27
NL7704570A (en) 1977-10-28
AU523259B2 (en) 1982-07-22
AU2440777A (en) 1979-03-08

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