EP1689761A2

EP1689761A2 - Chiral di- and triphosphites

Info

Publication number: EP1689761A2
Application number: EP04802710A
Authority: EP
Inventors: Manfred Theodor Reetz; Andreas Meiswinkel; Gerlinde Mehler
Original assignee: Studiengesellschaft Kohle gGmbH
Current assignee: Studiengesellschaft Kohle gGmbH
Priority date: 2003-11-12
Filing date: 2004-11-11
Publication date: 2006-08-16
Also published as: WO2005047299A3; DE10352757A1; CA2546218A1; JP2007512245A; US20060224002A1; WO2005047299A2

Abstract

The invention claims chiral di- and triphosphites of general formulas (I) or (II), which are bridged by suitable groups. The claimed compounds can be used in asymmetric transition metal catalysis and as chiral transition metal catalysts.

Description

Chiral di- and triphosphites

The present invention relates to chiral di- and triphosphites with the general formulas I or II, which are bridged via suitable groups, the use of these compounds in asymmetric transition metal catalysis, and chiral transition metal catalysts.

State of the art

Enantioselective transition metal-catalyzed processes have gained industrial importance in the past 20 years. B. the transition metal-catalyzed asymmetric hydrogenation. The ligands required for this are often chiral phosphorus-containing ligands (P ligands), e.g. As phosphines, phosphonites, phosphinites, phosphites or phosphoramidites, which are bound to the transition metals. Typical examples are rhodium, ruthenium or iridium complexes of optically active diphosphines such as BINAP.

The development of chiral ligands requires an expensive process consisting of "design" and "trial and error". A complementary search method is the so-called combinatorial asymmetric catalysis, in which libraries of modular chiral ligands or catalysts are produced and tested, which increases the likelihood of finding a hit. A disadvantage of all of these systems is the relatively high preparative effort in the preparation of large numbers of ligands and the often insufficient enantioselectivity that is observed in catalysis. It is therefore still the goal of industrial and academic research to produce new, inexpensive and particularly powerful ligands in the simplest possible way.

While most chiral phosphorus-containing ligands are chelating diphosphorus compounds, especially diphosphines, which bind the respective transition metal as a chelate complex, stabilize and thereby determine the extent of the asymmetric induction in catalysis, it has been known for some time that certain chiral monophosphonites , Monophosphite and Monophosphoramidite can also be efficient ligands, such. B. in the rhodium-catalyzed asymmetric hydrogenation of prochiral olefins. Well-known examples are BINOL-derived representatives such as B. the Ligands A, B and C. Spectroscopic and mechanistic studies indicate that two mono-P ligands are bound to the metal in catalysis. For this reason, the metal-ligand ratio is usually 1: 2. Some chiral monophosphanes of the type R ¹ R ² R ³ P can also be good ligands in transition metal catalysis, although they are generally expensive.

A a) R = = CH ₃ B a) R = CH ₃ C a) R = CH ₃ b) R ^: = C ₂ H ₅ b) R = C ₂ H ₅ b) R = CH (CH ₃ ) ₂ c ) R = = cC ₆ H- _| ic) R ⁼ c-CgH -) -) d) R = = C (CH ₃ ) ₃ d) R = C (CH ₃ ) ₃ e) R ^: ⁼ C ₆ H ₅ e) R = C ₆ H ₅ f ) R ^: = CI f) R = 2,6- (CH ₃ ) ₂ -C ₆ H ₃ g) R = CH (CH ₃ ) ₂ h) R = 9-fluorenyl

Monophosphorus-containing ligands of types A, B and C are particularly easily accessible and can be varied very easily due to the modular structure. By varying the

The radical R in A, B or C can be used to build up a large number of chiral ligands, which enables ligand optimization in a given transition metal-catalyzed reaction (e.g. hydrogenation of a prochiral olefin, ketone or imine or hydroformylation of a prochiral olefin). Unfortunately, there are limits to the method here, too. H. many substrates are implemented with moderate or poor enantioselectivity, e.g. B. in hydrogenations or hydroformylations. Therefore, there is still a need for new, inexpensive and effective chiral ligands for industrial use in transition metal catalysis.

The object of the present invention was accordingly to provide new chiral phosphorus ligands which are simple to prepare and which, as ligands in transition metal complexes, give catalysts which show high efficiency in transition metal catalysis, in particular in the hydrogenation and hydroboration and hydrocyanation of olefins, ketones and ketimes.

The present invention accordingly relates to chiral compounds having the general formula I or II

wherein L ¹ , L ² , L ³ , L ⁴ , L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ^{6 can} each be the same or different and at least one of L ¹ , L ² , L ³ and L ⁴ in formula I or at least one of L ¹ , L ² , L ³ , L ⁴ ,

L ⁵ and L ⁶ in formula II represent a chiral radical, it being possible for L ¹ and L ² , L ³ and L ⁴ , L ¹ and L ² , L ³ and L ⁴ , and L ⁵ and L ^{6 to} be linked to one another,

Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ^{1 '} , Y ^2' , Y ^{3 '} , Y ^4' , Y ^{5 '} , Y ^6' , Y ⁷ Y ⁸ Y ^{9 are the} same or can be different and represent O, S or a group NR ', in which R' is hydrogen, optionally substituted CC ₆ -

Alkyl or optionally substituted aryl means, where the substituents can be selected, for example, from F, Cl, Br, I, OH, NO ₂ , CN, carboxyl, carbonyl, sulfonyl, silyl,

CF ₃ , NR ^a R ^b , in which R ^a and R can be defined as R ¹ ,

R ¹ and R ² for C ₂ -C ₂₂ alkylene, preferably ethylene, n-propylene, iso-propylene, n-butylene, iso-butylene, sec-butylene, phenylene, diphenylene, which may optionally have substituents, such as

F, Cl, Br, I, OH, NO ₂ , CN, CF ₃ , NH ₂ , sulfonyl, silyl, mono- or di (CC ₆ ) alkylamino, C Ce

Alkyl, CrC ₆ -alkoxy, carboxyl or carbonyl, which may in turn optionally have substituents, and m and m 'represent a number between 1 and 1000, with the proviso that if one of Y ⁵ and Y ⁶ O and the other is N (CH ₂ CH ₃ ) and the

Groups L ¹ Y ¹ and L ² Y ² and L ³ Y ³ and L ⁴ Y ⁴ each together form a binol radical and m is 1, R ^{1 is} not ethylene, and when Y ⁵ and Y ^{6 are} O and the groups L ¹ Y ¹ and L ² Y ² and L ³ Y ³ and L ⁴ Y ⁴ each together form a binol radical, m is not 4 or 5, and if in the compound with the formula I the group Y ⁵ - [R ¹ Y ⁶ ] _m for -N (CH ₃ ) -C ₂ H ₄ -

N (CH ₃ ), -N (CH (CH ₃ ) ₂ ) -C ₃ H ₆ -N (CH (CH ₃ ) ₂ ) or -N (CHPhCH ₃ ) -C ₃ H ₆ -N (CHPhCH ₃ ) . The groups L ¹ Y ¹ and L ² Y ² as well as L ³ Y ³ and L'V do not together form a binol residue.

The compounds of the formulas I and II according to the invention are new. They can be easily converted into the corresponding complexes using transition metal salts, which in turn are extremely well suited for transition metal catalysis.

The compounds of the formulas I and II are preferably derivatives of phosphorous acid or thiophosphorous acid, ie Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ^{1 '} , Y ^2' , Y ^{3 '} , Y ^4' , Y ⁵ , Y ⁷ Y ⁸ Y ⁹ mean oxygen or sulfur. In addition to their good selectivity in enantioselective transition metal-catalyzed hydrogenation, hydroboration and hydrocyanation, the starting compounds can be prepared in a simple manner or are commercially available at low cost.

According to the invention, at least one of the radicals L ¹ , L ² , L ³ , L ⁴ , L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ^{6 is} chiral, ie has one or more optically active elements. Those ligands which contain elements with axial chirality are particularly preferred.

In a preferred embodiment, the radicals L ¹ and L ² , L ³ and L ⁴ , L ¹ and L ² , L ³ and

L ⁴ , as well as L ⁵ and L ^{6 are} bridged, with particular preference forming a binol radical. Examples of suitable groups L ¹ -Y ¹ and L ² -Y ² , L ³ -Y ³ , L ⁴ -Y ⁴ , L ^r -Y ^r , L ^{2 '} -Y ^2' , L ^{3 '} -Y ^3' , L ⁴ -Y ^{4 '} , L ⁵ - Y ⁵ and L ^ Y ⁶ in which these residues are bridged are:

R = H, alkyl, aryl, sulfonyl R = H, alkyl, aryl, sulfonyl

X = F, Cl, Br, I X = F, Cl, Br, I R = alkyl, aryl, alkoxy, carboxyl

X = F, Cl, Br, I X = F, Cl, Br, I R = alkyl, aryl, alkoxy,

R = H, alkyl, aryl, sulfonyl R = H, alkyl, aryl, sulfonyl carboxyl R ^' = H, alkyl, aryl, sulfonyl

X = F, Cl, Br, I X = F, Cl, Br, I R = alkyl, aryl, alkoxy,

R = H, alkyl, aryl, sulfonyl R = H, alkyl, aryl, sulfonyl

R = H, alkyl, aryl R = H, alkyl, aryl

R = H, alkyl, aryl R = H, alkyl, aryl X = F, Cl, Br, IR ^' = H, alkyl, aryl, sulfonyl R = H, alkyl, aryl, sulfonyl

R = H, alkyl, aryl R = H, alkyl, aryl R = H, alkyl, aryl

R ^' = H, alkyl, aryl, sulfonyl R ^' = H, alkyl, aryl, sulfonyl R ^' = H, alkyl, aryl, sulfonyl X = F, Cl, Br, I

X = F, Cl, Br, I R = H, alkyl, aryl R = H, alkyl, aryl

R = H, alkyl, aryl, sulfonyl R ^' = H, alkyl, aryl, sulfonyl R ^' = H, alkyl, aryl, sulfonyl X = F, Cl, Br, I R = alkyl R = H, alkyl, aryl, sulfonyl R = H, alkyl, aryl, sulfonyl

R = aryl

The groups -Y ⁵ - [R ^1γ6 ] _m - and -Y ⁵ - [R ^2γ6 ] m- connect the two chiral phosphorus-containing parts of the molecule to one another, thereby representing alkyleneoxy, thioalkyleneoxy or di- or triamino compounds. Y ⁶ and Y ⁶ for oxygen, so that the groups mentioned are radicals which are derived from mono-, di-, oligo- or polyalkylene oxide radicals or polyalkyleneoxy radicals. The groups R ¹ ^ and R ³ are preferably derived from ethylene oxide (EO), iso-propylene oxide (PO) and glycerol.

In the general formulas I and II, m and m 'according to the invention stand for numbers between 1 and 1000, preferably for 1 to 10, in particular 1 to 6. In particular if the radicals

R ¹ and R ^{2 are} ethylene, n-propylene or iso-propylene, m and m 'can represent a number above 6.

The present invention further provides a process for the preparation of chiral compounds of the general formula I or II,

in which

L ¹ , L ² , L ³ , L ⁴ , L ^{1 '} , L ^2' , L ^{3 '} , L ^4' , L ⁵ , L ⁸ , Y, Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁸ , Y ^{1 '} , Y ^2' , Y ^{3 '} , Y ^4' , Y ^{5 '} , Y ^8' , Y ⁷ Y ⁸ Y ⁹ , R ¹ ,

R ² , m and m 'are as defined above, wherein compounds having the following general formula IM

in the

Lg ¹ and Lg ^{2 can be the} same or different and selected for a group from L ¹ -Y ¹ ,

L ² _γ ² , _L ³ -Y ³ , L ⁴ -Y ⁴ , L ¹ -Y ^{1 '} , L ^2' -Y ^{2 '} , L ³ -Y ^3' , L ⁴ -Y ^{4 '} , L ⁵ -Y ⁸ or L ⁶ -Y ⁹ , in the presence of a base of a compound of the general formula IV or VH -Y ⁵ - [RV] - H (IV)

H - Y ^{5 '} - [RV ^' j _π v - H (V)

to be reacted.

In a further possible embodiment for the preparation of the compounds according to the invention having the formulas I or II, compounds having the general formula VI or VII CI ₂ P- Y ⁵ - [RVL -PCI ₂ (VI)

CI ₂ P- Y ^{5 '} - [RV ^' j _m -PCI, (VII) PCI ₂ implemented with ligands of the formula Lg ¹ or Lg ² to form compounds of the general formulas I or II.

In order to obtain compounds of the formula I or II according to the invention with at least one chiral center, at least one of the compounds with the formulas III to XII has a chiral center or axial chirality. The pure or enriched enantiomers are preferably used as starting compounds. Enantiomeric mixtures of the compounds of the formula I or II according to the invention can be separated into the pure enantiomers in a manner known per se by physical and chemical separation processes. Chromatography may be mentioned as physical separation processes. The chemical separation can be carried out by co-crystallization with suitable chiral, enantiomerically enriched auxiliaries, such as, for example, chiral enantiomerically pure amines.

If one or more of the radicals L ¹ to L ^{8 are} aryl radicals or bridged aryl radicals, the separation of stereoisomers can take place, for example, by the compounds of the formula I or II being co-crystallized with suitable chiral, enantiomerically enriched auxiliaries, such as, for example, chiral enantiomerically pure amines into which enantiomers are separated.

The present invention further relates to transition metal catalysts which contain chiral compounds of the general formula I and / or II as ligands.

The present invention further relates to a process for the preparation of transition metal catalysts comprising transition metal complexes of chiral compounds of the general formula I and / or II, in which transition metal salts are known per se with one or more of the compounds of the formulas I and / or II are implemented.

The catalysts or precatalysts can be prepared by processes which are well known to those skilled in the art. The respective ligands or mixtures of ligands are usually brought together with a suitable transition metal complex. The transition metals that can be used include those from groups IIIb, IVb, Vb, Vlb, Vllb, VIII, Ib and Mb of the periodic table, as well as lanthanides and actinides. The metals are preferably selected from the transition metals of the

Groups VIII and Ib of the periodic table. In particular, these are Transition metal complexes of ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum and copper, preferably those of ruthenium, rhodium, iridium, nickel, palladium, platinum and copper.

The transition metal complexes can be common salts such as MX _n (X = F, Cl, Br, I, BF ₄ ^" , BAr ₄ ^" , where Ar is phenyl, benzyl or 3,5-bistrifluoromethylphenyl, SbF ₆ ^" , PF ₆ ^" , CIO ₄ ^" , RCO ', CFaSOa", Acac "), for example [Rh (OAc) ₂ ] ₂ , Rh (acac) ₃ , Rh (COD) ₂ BF ₄ , Cu (CF ₃ SO ₃ ) ₂ , CuBF ₄ , Ag (CF ₃ SO ₃ ), Au (CO) CI, ln (CF ₃ SO ₃ ) ₃ , Fe (CIO ₄ ) ₃ , NiCI ₂ (COD) (COD = 1, 5-cyclooctadiene), Pd (OAc) ₂ , [C ₃ H ₅ PdCI] ₂ , PdCI ₂ (CH ₃ CN) ₂ or La (CF ₃ SO ₃ ) ₃ , to name but a few, but they can also be metal complexes, which carry ligands such as olefins, dienes, pyridine, CO or NO (to name just a few), the latter being completely or partially displaced by the reaction with the P ligands. Cationic metal complexes can also be used Variety of options (G. Wilkinson, Comprehensive Coordination Chemistry, Pergamon Press, Oxford (1987); B. Cornils, WA Herrmann, Applied Homogeneous Catalysis with

Organometallic Compounds, VCH, Weinheim (1996)). Common examples are Rh (COD) ₂ BF ₄ , [(Cymol) RuCI ₂ ] ₂ , (pyridine) ₂ lr (COD) BF ₄ , Ni (COD) ₂ , (TMEDA) Pd (CH ₃ ) ₂ (TMEDA = N , N, ΛT, ΛT-tetramethylethylenediamine), Pt (COD) ₂ , PtCI ₂ (COD) or [RuCI ₂ (CO) ₃ ] ₂ , to name just a few.

The metal compound and the ligand, i.e. Compounds with the formula I or II are usually used in amounts such that catalytically active compounds are formed. For example, the amount of the metal compound used can be 25 to 200 mol%, based on the chiral compounds of the general formulas I and / or II used, 30 to 100 mol% are preferred, 80 to 100 mol% are very particularly preferred, and more more preferably 90 to 100 mol%.

The catalysts, which contain transition metal complexes or isolated transition metal complexes generated in situ, are particularly suitable for use in a process for the preparation of chiral compounds. The catalysts are preferably used for asymmetric 1,4-additions, asymmetric hydroformylations, asymmetric hydrocyanations, asymmetric hydroboration, asymmetric hydrosilylation, asymmetric hydrovinylation, asymmetric Heck reactions and asymmetric hydrogenations. Another subject is accordingly a process for asymmetric transition metal-catalyzed hydrogenation, hydroboration, hydrocyanation, 1,4-addition, hydroformylation, hydrosilylation, hydrovinylation and Heck reaction of prochiral olefins, ketones or ketimines, characterized in that the catalysts contain chiral ligands have the formulas I and / or II defined above.

In a preferred embodiment of the present invention, the transition metal catalysts are used for the asymmetric hydrogenation, hydroboration or hydrocyanation of prochiral olefins, ketones or ketimines. End products are obtained in good yield and high purity of the optical isomers.

Preferred asymmetric hydrogenations are, for example, hydrogenations of prochiral C = C bonds such as, for example, prochiral enamines, olefins and enol ethers, C = O bonds such as, for example, prochiral ketones and C = N bonds such as, for example, prochiral imines. Particularly preferred asymmetric hydrogenations are hydrogenations of prochiral enamines and olefins.

The amount of the metal compound or the transition metal complex used can be, for example, 0.0001 to 5 mol%, based on the substrate used, 0.0001 to 0.5 mol% is preferred, 0.0001 to 0.1 is very particularly preferred mol% and even more preferably 0.001 to 0.008 mol%.

In a preferred embodiment, asymmetric hydrogenations can be carried out, for example, in such a way that the catalyst is generated in situ from a metal compound and a chiral compound of the general formula I and / or II, if appropriate in a suitable solvent, the substrate is added and the reaction mixture is brought down at the reaction temperature Hydrogen pressure is set.

To carry out a hydrogenation z. B. dissolved in a heated autoclave metal compound and ligand in degassed solvent. The mixture is stirred for about 5 minutes and then the substrate is added in degassed solvent. After the respective temperature has been set, the mixture is hydrogenated with H ₂ overpressure.

Suitable solvents for the asymmetric hydrogenation are, for example, chlorinated alkanes such as methylene chloride, short-chain CC ₆ alcohols, such as. As methanol, iso-propanol or ethanol, aromatic hydrocarbons, such as. B. toluene or benzene, ketones such as z. B. acetone or carboxylic acid esters such. B. ethyl acetate.

The asymmetric hydrogenation is carried out, for example, at a temperature of from -20 ° C. to 200 ° C., preferably 0 to 100 ° C. and particularly preferably at 20 to 70 ° C.

The hydrogen pressure can be, for example, 0.1 to 200 bar, preferably 0.5 to 50 and particularly preferably 0.5 to 5 bar.

The catalysts of the invention are particularly suitable in a process for the production of chiral active ingredients of pharmaceuticals and agricultural chemicals or

Intermediate products of these two classes.

The advantage of the present invention is that good activities with extraordinary selectivity can be achieved with ligands that are easy to prepare, especially in asymmetric hydrogenations.

Examples

Preparation of Chiral Di- and Triphosphite Ligands Example 1. Synthesis of Bis-O - [(R) -4H-dinaphtho [2,1-d: 1 ^' , 2'-f] - [1, 3,2] dioxaphosphepin-4 , 4 ^' - diyl] -1, 2-ethanediol (I: L ¹ Y ¹ and L ² Y ² = L ³ Y ³ and L ⁴ Y ⁴ = BINOL; Y ⁵ = O; R ¹ Y * = (CH ₂ CH ₂ O); m = 1)

0.93 g (2.65 mmol) (/ ^^ - binaphthylphosphoric acid diester chloride were initially introduced into 150 ml of absolute diethyl ether at room temperature. 74 μl (0.082 g, 1.32 mmol) of absolute 1, 2-ethanediol and 0.41 ml (0.29 g, 2.91 mmol ) After stirring overnight, the precipitated colorless solid was filtered off over a D4 frit and washed with 5 ml of absolute diethyl ether. The filtrate was then completely freed from the solvent. 0.71 g (1.03 mmol, 77.9%) was obtained. Product as colorless powder Analysis: ¹ H-NMR (CD ₂ CI ₂ , 300 MHz) 7.91-7.15 [24H], 3.92 (m) [2H], 3.71 (m) [2H], ¹³ C-NMR (CD ₂ CI ₂ , 75 MHz) 63.62 (t) J = 4.8 Hz; ³¹ P-NMR (CD ₂ CI ₂ , 121 MHz) 141.53 (s); MS (El,

Evaporation temperature 275 ° C) m / z = 690 (17.29%), 268 (100%), 239 (38.82%) EA P: 8.39% (calc. 8.97%).

Example 2. Synthesis of bis-O - [(S) -4H-dinaphtho [2,1-d: 1 ', 2'-f] - [1, 3,2] dioxaphosphepin-4,4 ^' - diyl] - 1,3-propanediol (I: L ¹ Y ¹ and L ² Y ² = L ³ Y ³ and L ⁴ Y ⁴ = BINOL; Y ⁵ = O; Y ⁵ = O; R ¹ Y ⁶ =

(CH ₂ CH ₂ CH ₂ O); m = 1)

1.97 g (5.62 mmol) of (S) -2,2 ^{'-Binaphthylphoshorigsäurediesterchlorid} were abs ml at room temperature in the 150th Diethyl ether submitted. For this purpose, 200 ul (0.21 g, 2.81 mmol) abs. 1,3-propanediol and 0.86 ml (0.62g, 6.18 mmol) abs. Pipetted triethylamine. After stirring overnight, the colorless solid which had precipitated out was filtered off over a D4 frit and washed with 5 ml of abs. Washed diethyl ether. The filtrate was then completely freed from the solvent. 1.6 g (2.27 mmol, 81.1%) of product were obtained as a colorless powder. Analysis: ¹ H NMR (CD ₂ CI ₂ , 300 MHz) 7.90-7.12 [24H], 3.84 (m) [4H], 1.69 (m) [2H]; ¹³ C NMR (CD ₂ CI ₂ , 75 MHz) 60.43 (d) J = 6.8 Hz, 31.38; ³¹ P NMR (CD ₂ CI ₂ , 121 MHz) 141.92 (s); MS (El,

Evaporation temperature 280 ° C) m / z = 704 (22.11%), 373 (100%), 268 (91.9%); EA P: 7.99% (calc. 8.79%).

Example 3. Synthesis of (S, S) bis-O - [(S) -4H-dinaphtho [2,1-d: 1 ', 2'-f] - [1, 3,2] dioxaphosphepin-4 , 4 ^" -diyl] - 1,4-butanediol (I: L ¹ Y ¹ and L ² Y ² = L ³ Y ³ and L ⁴ Y ⁴ = BINOL; Y ⁵ = O; RV =

(CH ₂ CH ₂ CH ₂ CH ₂ O), m = 1) 1.10 g (3.13 mmol) of (S) -2,2 ^{'-Binaphthylphoshorigsäurediesterchlorid} were abs ml at room temperature in the 150th Diethyl ether submitted. For this, 140 μl (0.14 g, 1.56 mmol) abs. 1, 4-butanediol and 0.48 ml (0.35g, 3.44 mmol) abs. Pipetted triethylamine. After stirring overnight, the colorless solid which had precipitated out was filtered off on a D4 frit and filtered with

5 ml abs. Washed diethyl ether. The filtrate was then completely freed from the solvent. 0.86 g (1.19 mmol, 76.7%) of product was obtained as a colorless powder. Analysis: H NMR (CD ₂ CI ₂ , 300 MHz) 7.90-7.18 [24H], 3.85 (m) [2H], 3.68 (m) [2H], 1.43 (m) [4H]; ¹³ C NMR (CD ₂ CI ₂ , 75 MHz) 63.87 (d) J = 6.9 Hz, 26.50 (d) J = 4.1 Hz; ³¹ P NMR (CD ₂ CI ₂ , 121 MHz) 142.72 (s); MS (El, evaporation temperature 285 ° C) m / z = 718 (15.05%), 268

(100%), 239 (50.5%); EA P: 8.06% (calc. 8.62%).

Example 4. Synthesis of 1, 7-bis-O - [(S) -4H-dinaphtho [2,1-d: 1 ', 2'-f] - [1, 3,2] dioxaphosphepine-4,4 ^, -diyl] -1, 4,7-trioxaheptane (I: L ¹ Y ¹ and L ² Y ² = L ³ Y ³ and L ⁴ Y ⁴ = BINOL; Y ⁵ = O; RV = (CH ₂ CH ₂ O) , m = 2)

0.86 g (2.45 mmol) (S ^^ - binaphthylphosphoric acid ester chloride were initially introduced into 150 ml of absolute diethyl ether at room temperature. 120 μl (0.13 g, 1.23 mmol) of absolute diethylene glycol and 0.37 ml (0.27 g, 2.69 mmol) of absolute triethylamine were added After stirring overnight, the colorless solid which had precipitated out was filtered off over a D4 frit and washed with 5 ml of absolute diethyl ether, and the filtrate was then completely freed from the solvent, giving 0.50 g (0.68 mmol, 55.3%) of the product as a colorless powder. Analysis: ¹ H-NMR (CD ₂ CI ₂ , 300 MHz) 7.89-7.14 [24H], 4.01 (m) [2H], 3.87 (m) [2H], 3.52 (m) [4H], ¹³ C-NMR (CD ₂ CI ₂ , 75 MHz) 69.89 (d) J = 5.0 Hz, 63.58 (d) J = 5.7 Hz; ³¹ P-NMR (CD ₂ CI ₂ , 121 MHz) 143.59 (s); MS (El, evaporation temperature 285 ° C) m / z = 734 (9.05%), 268

(100%), 239 (43.46%); EA C: 69.64% (calc. 71.93%), H: 5.15% (calc. 4.39%); P: 7.84% (calc. 8.43%).

Example 5. Synthesis of 1, 10-bis-O - [(S) -4H-dinaphtho [2,1-d: 1 ', 2'-f] - [1, 3,2] dioxaphosphepine-4,4 ^' -diyl] -1, 4,7,10-tetraoxadecane (I: L ¹ Y ¹ and L ² Y = L ³ Y ³ and L ⁴ Y ⁴ = BINOL; Y ⁵ = O; RV =

(CH ₂ CH ₂ O); m = 3)

0.88 g (2.50 mmol) of (S) -2.2 ^Λ- binaphthylphosphoric acid diester chloride were dissolved in 150 ml of abs. Diethyl ether submitted. For this purpose, 170 ul (0.188 g, 1.25 mmol) abs. Triethylene glycol and 0.38 ml (0.28 g, 2.76 mmol) abs. Pipetted triethylamine. To

The precipitated colorless solid was filtered off over a D4 frit while stirring overnight and with 5 ml abs. Washed diethyl ether. The filtrate was then completely freed from the solvent. 0.63 g (0.81 mmol, 64.7%) of product was obtained as a colorless powder. Analysis: ¹ H NMR (CD ₂ CI ₂ , 300 MHz) 7.86-7.12 [24H], 3.95 (m) [2H], 3.79 (m) [2H], 3.50 (s) [4H], 3.46 (m) [4H]; ¹³ C NMR (CD ₂ CI ₂ , 75 MHz) 69.90 (d) J = 3.9 Hz, 69.81 (s), 63.61 (d) J = 7.2 Hz; ³¹ P NMR (CD ₂ CI ₂ , 121 MHz) 143.84 (s); MS (El, evaporation temperature 275 ° C) m / z = 778 (8.66%), 376 (34.39%), 268 (100%), 239 (23.95%); EA P: 7.96% (calc. 7.19%).

Example 6. Synthesis of 1, 13-bis-O - [(S) -4H-dinaphtho [2,1-d: 1 ', 2'-f] - [1, 3,2] dioxaphosphepine-4,4 ^* -diyl] - 1, 4,7,10,13-pentaoxatridecan (I: L ¹ Y ¹ and L ² Y ² = L ³ Y ³ and L ⁴ Y ⁴ = BINOL; Y ⁵ = O; RV = (CH ₂ CH ₂ O); m = 4)

1.20 g (3.40 mmol) of (S) -2,2 ^' -Binaphthylphoshorigsäureesterchlorid were at room temperature in 150 ml abs. Diethyl ether submitted. For this purpose, 290 μl (0.33 g, 1.70 mmol) abs. Tetraethylene glycol and 0.52 ml (0.38 g, 3.74 mmol) abs. Pipetted triethylamine. After stirring overnight, the colorless solid which had precipitated out was filtered off over a D4 frit and washed with 5 ml of abs. Washed diethyl ether. The filtrate was then completely freed from the solvent. 0.95 g (1.15 mmol, 67.9%) of product was obtained as a colorless powder. Analysis: ¹ H-NMR (CD ₂ CI ₂ , 300 MHz) 7.87-7.16 [24H], 3.95 (m) [2H], 3.82 (m) [2H], 3.51 (s) [8H], 3.41 (m) [4H]; ¹³ C NMR (CD ₂ CI ₂ , 75 MHz) 70.27 (s), 69.78 (s), 69.57 (s), 63.67 (d) J = 7.1 Hz; ³¹ P NMR (CD ₂ CI ₂ , 121 MHz) 143.76 (s); MS (El, evaporation temperature 300 ° C) m / z = 376 (29.67%), 268 (100%), 239 (31.44%) EA P: 6.45% (calc. 7.52%).

Example 7. Synthesis of 1, 16-bis-O - [(S) -4H-dinaphtho [2,1-d: r, 2'-f] - [1, 3,2] dioxaphosphepine-4,4 ^' - diyl] -1, 4,7,10,13,16-hexaoxahexadecan (I: L ¹ Y ¹ and L ² Y ² = L ³ Y ³ and L ⁴ Y ⁴ = BINOL; Y ⁵ = O; RV = (CH ₂ CH ₂ O); m = 5)

0.86 g (2.44 mmol) of (S) -2,2 ^' -Binaphthylphoshorigsäureesterchlorid were at room temperature in 150 ml abs. Diethyl ether submitted. For this purpose, 260 μl (0.29g, 1.22 mmol) abs. Pentaethylene glycol and 0.38 ml (0.27 g, 2.70 mmol) abs. Pipetted triethylamine. After stirring overnight, the precipitated colorless solid was filtered off on a D4 frit and treated with 5 ml of abs. Washed diethyl ether. The filtrate was then completely freed from the solvent. 0.75 g (0.86 mmol, 70.9%) of product was obtained as a colorless powder. Analysis: ¹ H NMR (CD ₂ CI ₂ , 300 MHz) 7.89-7.13 [24H], 3.95 (m) [2H], 3.80 (m) [2H], 3.46 (s) [12H], 3.45 (m) [4H]; ¹³ C NMR (CD ₂ CI ₂ , 75 MHz) 71.70 (s), 69.81 (s), 69.69 (s), 69.51 (s), 63.65 (d); J = 7.2 Hz; ³¹ P NMR (CD ₂ CI ₂ , 121 MHz) 143.70 (s); MS (El, evaporation temperature 315 ° C) m / z = 376 (28.61%), 268 (100%), 239 (42.62%); EA P: 6.60% (calc. 14.7%).

Example 8. Synthesis of Bis-O - [(S) -4H-dinaphtho [2,1-d: r, 2'-f] - [1, 3,2] dioxaphosphepine-4,4 ^' - diyl] -1 , 2-dihydroxybenzene (I: L ¹ Y ¹ and L ² Y ² = L ³ Y ³ and L ⁴ Y ⁴ = BINOL; Y ⁵ = O; RV = C ₆ H ₅ O; m = 1)

0.73 g (2.07 mmol) (S ^^ - Binaphthylphoshorigsäureesterchlorid were placed at room temperature in 150 ml of absolute diethyl ether and 0.32 ml (0.23 g, 2.28 mmol) of absolute triethylamine. The solution was cooled to -80 ° C. 0.114 g (1,035 mmol) of 1,2-dihydroxybenzene in 20 ml of diethyl ether was added dropwise over the course of 1 hour and the suspension was warmed to room temperature, and after stirring overnight the precipitated colorless solid was filtered off on a D4 frit and washed with 5 ml of absolute diethyl ether The filtrate was then completely freed from the solvent, giving 0.54 g (0.73 mmol, 70.6%) of the product as a colorless powder.Analysis: ¹ H-NMR (CD ₂ CI ₂ , 300 MHz) 7.96-6.38 [28H]; ³¹ P-NMR (CD ₂ CI ₂ , 121 MHz) 145.65 (s); EA P: 7.71% (calc. 8.38%).

Example 9 Synthesis of Bis-O [(S) -4H-dinaphtho [2,1-d: 1 ', 2'-f] - [1, 3,2] dioxaphosphepin-4,4 ^' - diyl] -1, 3-dihydroxybenzene (I: L ¹ Y ¹ and L ² Y ² = L ³ Y ³ and L ⁴ Y ⁴ = BINOL; Y ⁵ = O; RV = C ₆ H ₅ O; m = 1)

0.44g (1.26 mmol) of (S) -2,2 ^{'-Binaphthylphoshorigsäureesterchlorid} were at room' temperature abs ml in 150th Diethyl ether submitted. For this purpose 0.07 g (0.63 mmol) 1, 3-di-hydroxybenzene and 0.19 ml (0.14 g, 1.38 mmol) abs. Pipetted triethylamine. After stirring overnight, the colorless solid which had precipitated out was filtered off over a D4 frit and washed with 5 ml of abs. Washed diethyl ether. The filtrate was then completely freed from the solvent. 0.29 g (0.39 mmol, 62.3%) of product was obtained as a colorless powder. Analysis: ¹ H NMR (CD ₂ CI ₂ , 300 MHz) 7.95-6.94 [28H]; ³¹ P NMR (CD ₂ CI ₂ , 121 MHz) 144.81; MS (El, evaporation temperature 285 ° C) m / z = 738 (63.22%), 315 (88.94%), 268 (100%), 239 (20.42%); EA P: 7.32% (calc. 8.38%).

Example 10. Synthesis of bis-O - [(S) -4-dinaphtho [2,1-d: 1 ', 2'-f] - [1, 3,2] dioxaphosphepin- ^4,4' -diyl] - 1,4-dihydroxybenzene (I: L ¹ Y ¹ and L ² Y ² = L ³ Y ³ and L ⁴ Y ⁴ = BINOL; Y ⁵ = O; RV = C ₆ H ₅ O; m = 1) 0.56 g ( 1.60 mmol) (S) -2,2 ^' -Binaphthylphoshorigsäureesterchlorid were at room temperature in 150 ml abs. Diethyl ether submitted. For this 0.088 g (0.80 mmol) 1, 4-di- hydroxybenzene and 0.24ml (0.18g, 1.76 mmol) abs. Pipetted triethylamine. After stirring overnight, the precipitated colorless solid was filtered off on a D4 frit and treated with 5 ml of abs. Washed diethyl ether. The filtrate was then completely freed from the solvent. 0.26 g (0.35 mmol, 44.0%) of product was obtained as a colorless powder. Analysis: ¹ H NMR (CD ₂ CI ₂ , 300 MHz) 8.13-7.29 [28H]; ³¹ P NMR (CD ₂ CI ₂ , 121 MHz) 145.44; MS (El,

Evaporation temperature 200 ° C) m / z = 738 (42.75%), 315 (100%), 268 (69.45%), 239 (15.08%); EA P: 7.67% (calc. 8.38%).

Example 11. Synthesis of bis-O - [(S) -4-dinaphtho [2,1-d: 1 \ 2'-f] - [1, 3,2] dioxaphosphepin- 4,4 ^'-diyl] -1 , 2-bis (hydroxymethyl) benzene (I: L ¹ Y ¹ and L ² Y ² = L ³ Y ³ and L ⁴ Y ⁴ = BINOL; Y ⁵ = O;

R ¹ Y ⁶ = CH ₂ C ₆ H ₅ CH ₂ O, m = 1)

1.0 g (2.85 mmol) of (S) -2,2 ^' -Binaphthylphoshorigsäureesterchlorid were at room temperature in 150 ml abs. Diethyl ether submitted. For this, 0.20g (1.42 mmol) of 1,2-bis (hydroxymethyl) benzene and 0.44 ml (0.32 g, 3.13 mmol) of abs. Pipetted triethylamine. To

Stirring overnight, the colorless solid which had precipitated was filtered off over a D4 frit and washed with 5 ml of abs. Washed diethyl ether. The filtrate was then completely freed from the solvent. 0.62 g (0.81 mmol, 57.0%) of product was obtained as a colorless powder. Analysis: ¹ H NMR (CD ₂ CI ₂ , 300 MHz) 7.87-7.09 [28H], 5.14 (m) [2H], 4.75 (m) [2H]; ¹³ C NMR (CD ₂ CI ₂ , 75 MHz) 63.37 (d) J = 6.4 Hz; ³¹ P NMR (CD ₂ CI ₂ , 121 MHz) 140.97 (s); EA P: 7.43%

(calculated 8.08%).

Example 12. Synthesis of bis-O - [(S) -4-dinaphtho [2,1-d: 1 ', 2'-f] - [1, 3,2] dioxaphosphepin- ^4,4' -diyl] - 1, 1 ^' -biphenol (IL ¹ Y ¹ and L ² Y ² = L ³ Y ³ and L ⁴ Y ⁴ = BINOL; Y ⁵ = O; RV = C ₆ H ₅ C ₆ H ₅ O)

1.1 g (3.10 mmol) of (S) -2.2 ^Λ- binaphthylphosphoric acid ester chloride were dissolved in 150 ml of abs. Diethyl ether submitted. For this purpose 0.29 g (1.55 mmol) 1, 1 ^* -Biphenol and 0.48 ml (0.34 g, 3.40 mmol) abs. Pipetted triethylamine. After stirring overnight, the precipitated colorless solid was filtered off on a D4 frit and treated with 5 ml of abs. Washed diethyl ether. The filtrate was then completely freed from the solvent. 1.03 g (1.26 mmol, 81.6%) of product were obtained as a colorless powder. Analysis: ¹ H NMR (CD ₂ CI ₂ , 300 MHz) 7.87-7.09 [32H]; ³ P NMR (CD ₂ CI ₂ , 121 MHz) 145.23 (s); MS (El, evaporation temperature 250 ° C) m / z = 814 (0.28%), 483 (100%), 268 (10.14%), 168 (18.62%); EA P: 7.15% (calc. 7.60%). Example 13. Synthesis of 4,4 ^* -Bis-O - [(S) -4H-dinaphtho [2,1-d: 1 \ 2'-f] - [1, 3,2] dioxaphosphepin-4, 4'-diyl] isopropylidene diphenol (I: L ¹ Y ¹ and LY ² = L ³ Y ³ and L ⁴ Y ⁴ = BINOL; Y ⁵ = O; RV = C ₆ H ₅ C (CH ₃ ) ₂ C ₆ H ₅ O)

0.68 g (1.94 mmol) of (S) -2,2 ^' -Binaphthylphoshorigsäureesterchlorid were at room temperature in 150 ml abs. Diethyl ether submitted. To this was added 0.22g (0.97 mmol) of 4,4 ^'-lso- propylidendiphenol and 0:30 ml (0.21g, 2.13 mmol) abs. Pipetted triethylamine. After stirring overnight, the precipitated colorless solid was filtered off on a D4 frit and treated with 5 ml of abs. Washed diethyl ether. The filtrate was then completely freed from the solvent. 0.63 g (0.73 mmol, 75.2%) of product was obtained as a colorless powder.

Analysis: ¹ H NMR (CD ₂ CI ₂ , 300 MHz) 7.90-6.98 [32H], 1.55 (s) [6H]; ³¹ P NMR (CD ₂ CI ₂ , 121 MHz) 145.21 (s); MS (El, evaporation temperature 325 ° C) m / z = 856 (41.56%), 841 (24.68%), 315 (100%), 268 (73.43%); EA P: 6.58% (calc. 7.23%).

Example 14. Synthesis of 1, 3,5-tris-O - [(S) -4H-dinaphtho [2,1-d: 1 ', 2'-f] - [1, 3,2] dioxaphosphepin- 4,4 ^'-diyl] - benzene (II: Y ¹ L ^1' and L ² Y ² = Y ³ L ³ and L ⁴ Y ⁴ = L ⁵ and L ⁶ Y ⁸ Y ⁹ = BINOL Y ⁵ = O; R ² Y ⁶ = C ₆ H ₃ O; m = 1)

1.15 g (3.28 mmol) of (S) -2,2 ^{'-Binaphthylphoshorigsäureesterchlorid} were temperature abs in 150 ml at room. Diethyl ether submitted. 0.137 g (1.09 mmol) 1, 3.5-

Trihydroxybenzene and 0.30 ml (0.36 g, 3.61 mmol) abs. Pipetted triethylamine. After stirring overnight, the precipitated colorless solid was filtered off on a D4 frit and treated with 5 ml of abs. Washed diethyl ether. The filtrate was then completely freed from the solvent. 0.92 g (0.86 mmol, 79.0%) of product was obtained as a colorless powder. Analysis: ¹ H NMR (CD ₂ CI ₂ , 300 MHz) 7.95-7.13 [36H], 6.77 (s) [3H]; ³¹ P NMR (CD ₂ CI ₂ ,

121 MHz) 144.06 (s); EA P: 8.29% (calc. 8.69%).

Example 15. Synthesis of Tris-O - [(S) -4H-dinaphtho [2,1-d: 1 ', 2'-f] - [1, 3,2] dioxaphosphepine-4,4-diyl] - 2,2 ^' , 2 "-nitrilotriethanol (II: L ¹ V ^1' and L ² Y ² = L ³ Y ³ and L ⁴ Y ⁴ = L ⁵ Y ⁸ and L ⁶ Y ⁹ = BINOL; Y ⁵ = Y ^{6 =} Y ⁷ O; R ² = N (C ₂ H ₄ ) ₃ ; m = 1)

1.26 g (3.60 mmol) of (S) -2,2 ^' -Binaphthylphoshorigsäureesterchlorid were at room temperature in 150 ml abs. Diethyl ether submitted. 160 μl (0.18 g, 1.2 mmol) triethanolamine and 0.55 ml (0.40 g, 3.95 mmol) abs. Pipetted triethylamine. After stirring overnight, the colorless solid which had precipitated out was filtered off on a D4 frit and filtered with

5ml abs. Washed diethyl ether. The filtrate was then completely from Free solvent. 1.02 g (0.93 mmol, 77.8%) of product was obtained as a colorless powder. Analysis: H NMR (CD ₂ CI ₂ , 300 MHz) 7.98-7.07 [36H], 3.71 (m) [6H], 2.59 (t) [6H] J = 5.7 Hz; ³¹ P NMR (CD ₂ CI ₂ , 121 MHz) 143.08 (s); EA P: 7.92% (calc. 8.51%).

Examples 16-18. General instructions for the synthesis of ligands that differ from

Derive amino alcohols

600 mg (1.71 mmol) of (S) -2,2'-binaphthylphosphoric acid ester chloride and 0.3 ml (2.16 mmol) of triethylamine were initially introduced into 100 ml of toluene at -78 ° C., and 0.5 equivalents (0.86 mmol) of the corresponding amino alcohol were added to each. After stirring for 16 h and warming to room temperature, the precipitate formed was filtered off and the filtrate was completely freed from the solvent. After drying under high vacuum, the ligands were isolated as white solids in yields between 42% and 99%.

Example 16. Bis-O - [(S) -4H-dinaphtho [2,1-d: r, 2'-f] - [1, 3,2] dioxaphosphepine-4,4'-diyl] -Λ / - methyl-2-aminoethanol (I: L ¹ Y ¹ and L ² Y ² = L ³ Y ³ and L ⁴ Y ⁴ = BINOL; Y ⁵ = NCH ₃ ; RV = (CH ₂ CH ₂ O); m = 1)

Analysis: ¹ H-NMR (C ₆ D ₆ , 300.1 MHz) δ = 7.70-6.90 (m) [24 H], 3.75 (m, 1 H), 3.48 (m) [1 H], 3.11 (m) [ 1 H], 2.67 (m) [1 H], 2.15 (d, J _PH = 5.3 Hz) [3 H]; ³¹ P NMR (C ₆ D ₆ , 121.5 MHz) 149.8

(s), 139.0 (s); MS (El, pos. Ions): m / z = 703 [M] ⁺ .

Example 17. Bis-Λ /, O - [(S) -4H-dinaphtho [2,1-d: 1 ', 2'-f] - [1, 3,2] dioxaphosphepin-4,4'-diyl] - 3-aminopropanol (I: L ¹ Y ¹ and L ² Y ² = L ³ Y ³ and L ⁴ Y ⁴ = BINOL; Y ⁵ = NH; R ¹ Y ⁸ = (CH ₂ CH ₂ CH ₂ O); m = 1)

Analysis: ¹ H NMR (C ₆ D ₆ , 400.1 MHz) 7.71-6.86 (m) [24 H]. 3.71 (m) [1 H], 3.52 (m) [1 H], 2.79-2.66 (m) [2 H], 2.60 (m) [1 H], 1.16 (m) [2 H] ; ³¹ P NMR (C ₆ D ₆ , 162.0 MHz) 153.9 (s), 139.4 (s); MS (El, pos. Ions) m / z = 703 [M] ⁺ ; EA C: 72.68% (calc. 73.40%), H: 4.80% (calc. 4.44%), N 1.67% (calc. 1.99%), P: 8.44% (calc. 8.80%).

Example 18. Bis-Λ /, O - [(S) -4H-dinaphtho [2,1-d: 1 ', 2'-f] - [1, 3,2] dioxaphosphepin-4,4'-diyl] - 4-aminobutanol (I: L ¹ Y ¹ and L ² Y ² = L ³ Y ³ and l_V = BINOL; Y ⁵ = NH; R ¹ Y ⁸ = (CH ₂ CH ₂ CH ₂ CH ₂ O); m = 1)

Analysis: Η NMR (C ₆ D ₆ , 400.1 MHz) 7.69-6.88 (m) [24 H], 3.70 (m) [1 H], 3.50 (m) [1 H], 2.63 (m) [1H], 2.55-2.41 (m) [2H], 1.12 (m) [2H], 1.04 (m) [2H]; ³¹ P NMR (C ₆ D ₆ , 162.0 MHz) 153.8 (s), 140.0 (s); MS (El, pos. Ions) m / z = 717 [M] ⁺ ; EA C 73.58% (calc. 73.64%), H 4.70% (calc. 4.63%), N 2.06% (calc. 1.95%), P 8.52% (calc. 8.63%). hydrogenation

General instructions for hydrogenation with catalyst prepared in situ

0.5ml of a 2mM solution of [Rh (cod) ₂ ] BF ₄ in dichloromethane was placed in a round bottom flask with a side tap. For this purpose, 0.5 ml of a 2 mM solution of the specified ligand and then 9.0 ml of a 0.11 M substrate solution in dichloromethane were added. The solution was then saturated with hydrogen and stirred under 1.3 bar hydrogen pressure for 20 h at room temperature. 2 ml of the solution thus obtained were filtered through silica (70-230 mesh, activity level I) and analyzed by gas chromatography.

Examples 19-36. Enantioselective hydrogenation of dimethylitconate

Examples 19-36 describe the hydrogenation of the substrate dimethyl itaconate to 2-methylsuccinic acid dimethyl ester according to the "General instructions for hydrogenation with catalyst prepared in situ". The exact reaction conditions and the conversions and enantioselectivities achieved are given in Table 1.

Table 1 Example ligand L conversion ee from example in% ^[al in% config. 19 1 83.0 48.4 (R) 20 2 43.7 37.6 (S) 21 3 95.6 93.4 (S) 22 4 96.8 96.8 (S) 23 5 37.9 56.4 (S) 24 6 97.4 95.8 (S) 25 7 23.1 6.4 (S) 26 8 7.0 5.4 (S) 27 9 95.5 84.6 (S) 28 10 99.1 91.0 (S) 29 11 88.6 49.6 (S) 30 12 8.2 10.6 (S) 31 13 88.6 49.6 (S) 32 14 5.1 30.8 (S) 33 15 1.8 43.0 (S) 34 16 83.0 34.6 (S) 35 17 100 82.4 (S) 36 18 100 86.6 (S)

[a] If the starting material was no longer detectable by gas chromatography, the conversion is 100%. Examples 37-41. Enantioselective hydrogenation of methyl 2-acetamidoacrylate

Examples 37-41 describe the hydrogenation of the substrate 2-acetamidoacrylic acid methyl ester to Λ / -acetylalanine methyl ester according to the “general instructions for hydrogenation with catalyst prepared in situ”. The exact reaction conditions and the conversions and enantioselectivities achieved are given in Table 2.

Table 2 Example ligand L conversion ee from example in% ^[al in% config. 37 3 100 69.6 (R) 38 4 100 78.8 (R) 39 16 98.0 rac. - 40 17 100 36.0 (R) 41 18 100 88.8 (R) [a] If the starting material was no longer detectable by gas chromatography, the conversion is 100%.

Examples 42-43. Enantioselective hydrogenation of methyl α-acetamido cinnamate

Examples 42-43 describe the hydrogenation of the substrate αr-acetamido cinnamic acid methyl ester to Λ / -acetylphenylalanine methyl ester according to the “general instructions for hydrogenation with catalyst prepared in situ”. The exact reaction conditions and the conversions and enantioselectivities achieved are given in Table 3.

Table 3 Example ligand L conversion ee from example in% ^[al in% config. 42 3 89.2 58.8 (R) 43 4 81.5 63.6 (R)

Examples 44-48. Enantioselective hydrogenation of oAcetamidostyrene

Examples 44-48 describe the hydrogenation of the substrate α-acetamidostyrene

Λ / acetyl-1-phenylethylamine. 0.5 ml of a 2 mM solution of [Rh (cod) ₂ ] BF _{4 was} added to 0.5 ml of a 2 mM ligand solution. After adding 2.0 ml of a 0.25 M substrate solution, the mixture was stirred at 60 bar hydrogen pressure for 20 h. 2 ml of the solution thus obtained were filtered through silica (70-230 mesh, activity level I) and analyzed by gas chromatography. The the exact reaction conditions and the conversions and enantioselectivities achieved are given in Table 4.

Table 4 Example ligand L conversion ee from example in% ^lal in% config. 44 3 72.1 78.4 (R) 45 4 67.7 76.4 (R) 46 16 100 19.2 (S) 47 17 100 56.0 (R) 48 18 100 62.6 (R)

[a] If the starting material was no longer detectable by gas chromatography, the conversion is 100%.

Examples 49-51. Enantioselective hydrogenation of 1-phenyl-vinyl acetate

Examples 49-51 describe the hydrogenation of the substrate acetic acid 1-phenyl vinyl ester to acetic acid 1-phenyl ethanol ester. 0.25ml of a 2mM ligand solution was mixed with 0.25ml of a 2mM solution of [Rh (cod) ₂ ] BF ₄ . After adding 1.0 ml of a 0.1 M substrate solution and 2.0 ml of dichloromethane, the mixture was stirred at 60 bar hydrogen pressure for 20 h. 2 ml of the solution thus obtained were filtered through silica (70-230 mesh, activity level I) and analyzed by gas chromatography. The exact reaction conditions as well as the conversions and enantioselectivities achieved are given in Table 5.

Table 5 Example ligand L conversion ee from example in% ^Ial in% config. 49 16 100 76.6 (S) 50 17 100 59.8 (S) 51 18 100 31.4 (S)

Claims

claims

Chiral compounds with the general formula I or II

wherein L ¹ , L ² , L ³ , L ⁴ , L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ^{6 can} each be the same or different and at least one of L ¹ , L ² , L ³ and L ⁴ in formula I or at least one of L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ in formula II represent a chiral radical, where L ¹ and L ² , L ³ and L ⁴ , L ¹ and L ² , L ³ and L ⁴ , and L ⁵ and L ⁸ can be connected to one another, Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ^{1 '} , Y ^2' , Y ^{3 '} , Y ^{4 '} , Y ^5' , Y ^{6 '} , Y ⁷ Y ⁸ Y ^{9 may be the} same or different and represent O, S or a group NR' in which R 'is hydrogen, optionally substituted CrC ₆ alkyl or, if appropriate substituted aryl, where the substituents can be selected, for example, from F, Cl, Br, I, OH, NO ₂ , CN, carboxyl, carbonyl, sulfonyl, silyl, CF ₃ , NR ^a R ^b , where R ^a and R are like R ¹ can be defined, R ¹ and R ² for C ₂ -C ₂₂ alkylene, preferably ethylene, n-propylene, iso-propylene, n-

Butylene, isobutylene, sec-butylene, phenylene, diphenylene, which may optionally have substituents, such as F, Cl, Br, I, OH, NO ₂ , CN, CF ₃ , NH ₂ , sulfonyl, silyl, mono- or di (C ₁ -C ₆ ) alkylamino, CrC ₆ alkyl, CC ₆ alkoxy, carboxyl or carbonyl, which in turn may optionally have substituents, and m and m 'represent a number between 1 and 1000, with the proviso that when one of Y ⁵ and Y ^{6 is} O and the other is N (CH ₂ CH ₃ ) and the groups L ¹ Y ¹ and L ² Y ² and L ³ Y ³ and L ⁴ Y ^{4 are} each together form a binol residue and m is 1, R ^{1 is} not ethylene, and when Y ⁵ and Y ^{8 are} O and the groups L ¹ Y ¹ and L ² Y ² and L ³ Y ³ and L ⁴ Y ⁴ each together form a binol residue form, m is not 4 or 5, and if in the compound with the formula I the group Y ⁵ - [RV] ™ for -N (CH ₃ ) - C ₂ H ₄ -N (CH ₃ ), -N (CH (CH ₃ ) ₂ ) -C ₃ H ₆ -N (CH (CH ₃ ) ₂ ) or -N (CHPhCH ₃ ) -C ₃ H ₆ - N (CHPhCH ₃ ), the groups L ¹ Y ¹ and L form ² Y ² as well as L ³ Y ³ and LV do not together form a binol residue.

Compounds according to claim 1, characterized in that the groups R ¹ Y * and R ² Y ⁶ are derived from ethylene oxide or propylene oxide.

Compounds according to claim 1 or 2, characterized in that L ¹ and L ² , and L 4, i LV and L 2,, L 3 'and L, and L and L are bridged.

5. Compounds according to any one of claims 1 to 3, characterized in that Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁸ , Y ^{1 '} , Y ^2' , Y ^{3 '} , Y ^4' , Y ^{5 '} , Y ^8' , Y ⁷ Y ⁸ Y ⁹ mean oxygen or sulfur.

6. Compounds according to claim 5, characterized in that the bridged ligands are selected from

R = H, alkyl, aryl, sulfonyl R = H, alkyl, aryl, sulfonyl

X = F, Cl, Br, I X = F, Cl, Br, I R = alkyl, aryl, alkoxy, carboxyl

X = F, Cl, Br, I X = F, Cl, Br, I R = alkyl, aryl, alkoxy,

R = H, alkyl, aryl, sulfonyl R = H, alkyl, aryl, sulfonyl

R = H, alkyl, aryl X = F, Cl, Br, I R = H, alkyl, aryl

R = H, alkyl, aryl R = H, alkyl, aryl R = H, alkyl, aryl

X = F, Cl, Br, I R = H, alkyl, aryl R = H, alkyl, aryl

R = H, alkyl, aryl, sulfonyl R ^' = H, alkyl, aryl, sulfonyl R ^' = H, alkyl, aryl, sulfonyl X = F, Cl, Br, I

R = alkyl R = H, alkyl, aryl, sulfonyl R = H, alkyl, aryl, sulfonyl

R = aryl

Process for the preparation of compounds of general formula I or II,

l \ Y! X \ P- Y '- tR], - P _s X (i), /, Y ² L ⁴

in which

L ¹ , L ² , L ³ , L ⁴ , L ^{1 '} , L ^2' , L ^{3 '} , L ^4' , L ⁵ , Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁸ , Y ^r , Y ^{2 '} , Y ^3' , Y ^{4 '} , Y ^5' , Y ^{6 '} , Y ⁷ Y ⁸ Y ⁹ ,

R ¹ , R ² , m and m 'are as defined above, wherein compounds having the following general formula MI g ¹ PCI (III) Lg ² in which Lg ¹ and Lg ^{2 can be the} same or different and selected for a group from L ¹ _ γ L ² - Y ² , L ³ - Y ³ , L ⁴ - Y ⁴ , L - Y ^{1 '} , L ^2' - Y ^{2 '} , L ^3' - Y ^{3 '} , L ^4' - Y ^{4 '} , L ⁵ - Y ⁸ , or L ⁸ - Y ⁹ , in the presence of a base of a compound with the general formula IV or V

H -Y ⁵ - [R ¹ Y ⁸ ] _m - H (IV)

H - Y ^{5 '} - [R ² Y ^6' ] _m . - H (V) are reacted.

8. Process for the preparation of compounds of the general formula I or II,

■ 1 ■ 3 N '- Y ¹ _s P_ γ ⁵ _ [ _R ¹ γ ^β j _m _ p (|) ι 2 X \. 4

³ Yl \, \ / 5 ', 2 _{\ /} δ'ι / Y ³ ; p- γ - [RΎ ° W -P (ii). .7. L 'L ²

in which L ¹ , L ² , L ³ , L ⁴ , L ^{1 '} , L ^2' , L ^{3 '} , L ^4' , L ⁵ , Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ^{1 '} , Y ^2' , Y ^{3 '} , Y ^4' , Y ^{5 '} , Y ^6' , Y ⁷ Y ⁸ Y ⁹ , R ¹ , R ² , m and m 'as defined above, compounds with the general formula VI or VII

CI ₂ P- Y ⁵ - [R ¹ Y ⁸ ] _m -PCI ₂ (VI) CI ₂ P- Y ^{5 '} - [R ² Y ⁶ ] _m -PCI ₂ (VII) I PCI ₂ with ligands of the formula Lg ¹ or Lg ² are reacted to form compounds of the general formulas I or II.

9. Catalysts containing transition metal complexes of chiral compounds with the formula I and / or II, ¹ χ ^" Yl Y ³ P_ γ ⁵ _ r _R γ ⁶ ] _m - p; (la),"

(Ma)

wherein L ¹ , L ² , L ³ , L ⁴ , L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ^{8 can} each be the same or different and at least one of L ¹ , L ² , L ³ and L ⁴ in formula I or at least one of L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ⁶ in formula II represent a chiral radical, where L ¹ and L ² , L ³ and L ⁴ , L ¹ and L ² , L ³ and L ⁴ , and L ⁵ and L ⁶ can be connected to one another, Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ^{1 '} , Y ^2' , Y ^{3 '} , Y ^{4 '} , Y ^5' , Y ^{8 '} , Y ⁷ Y ⁸ Y ^{9 may be the} same or different and represent O, S or a group NR' in which R 'is hydrogen or optionally substituted CC ₆ alkyl, if necessary substituted aryl, where the substituents can be selected, for example, from F, Cl, Br, I, OH, NO ₂ , CN, carboxyl, carbonyl, sulfonyl, silyl, CF ₃ , NR ^a R ^b , where R ^a and R ^b as R 'can be defined, R ¹ and R ² for C ₂ -C ₂₂ alkylene, preferably ethylene, n-propylene, iso-propylene, n-butylene, iso-butylene, sec-butylene, phenylene, diphe nylene, which may optionally have substituents, such as F, Cl, Br, I, OH, NO ₂ , CN, NH ₂ , mono- or di (CC ₆ ) alkylamino, CC ₆ alkyl, CC ₆ alkoxy, carboxyl , which in turn can have substituents, are and m and nϊ represent a number between 1 and 1000.

10. A process for the preparation of transition metal catalysts containing transition metal complexes of chiral compounds of the general formula Ia and / or Ila, in which transition metal salts are reacted in a manner known per se with chiral compounds of the formulas I and / or II.

11. The method according to claim 10, characterized in that the transition metal salts are selected from transition metals of groups VIII and Ib of the periodic table.

12. A process for asymmetric transition metal-catalyzed hydrogenation, hydroboration, hydrocyanation, 1, 4 addition, hydroformylation, hydrosilylation, hydrovinylation and Heck reaction of prochiral olefins, ketones or ketimines, characterized in that the catalysts have chiral ligands with the following formulas I and / or II

(La)

(IIa)

in which L ¹ , L ² , L ³ , L ⁴ , L ^{1 '} , L ^2' , L ^{3 '} , L ^4' , L ⁵ , Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ^{1 '} , Y ^2' , Y ^{3 '} , Y ^4' , Y ^{5 '} , Y ^6' , Y ⁷ Y ⁸ Y ⁹ R ¹ , R ² , m and m 'as defined in claim 9.

13. The method according to claim 12, characterized in that the catalyst is selected from the following complexes, in which Z is an anion from the series BF ₄ ^" , BAr ₄ ^" , SbF ₆ ^" , and PF ₆ ^" , where Ar is phenyl, benzyl or 3,5-bistrifluoromethylphenyl.

14. A process for the preparation of chiral compounds in which the prochiral precursor is selected from olefins, ketones or ketimines, in the presence of a transition metal catalyst for hydrogenation, hydroboration or hydrocyanation 1, 4 addition, hydroformylation, hydrosilylation, hydrovinylation and Heck reactions is subjected to, characterized in that the transition metal catalyst has ligands which are selected from compounds with the general formulas I and / or II.