Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
  • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
  • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
  • B01J31/1855—Triamide derivatives thereof
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
  • B01J31/1865—Phosphonites (RP(OR)2), their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
  • B01J31/1865—Phosphonites (RP(OR)2), their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
  • B01J31/187—Amide derivatives thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
  • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
  • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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  • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
  • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
  • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
  • B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
  • B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
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  • C07C67/00—Preparation of carboxylic acid esters
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  • 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
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  • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
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  • C07F9/65683—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine
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  • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
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  • C07F9/6574—Esters of oxyacids of phosphorus
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  • B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
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• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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  • Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
  • Y10S502/506—Method of making inorganic composition utilizing organic compound, except formic, acetic, or oxalic acid or salt thereof

Definitions

• the present invention includes the surprising finding that mixtures of two or more chiral monophosphorus compounds (ie compounds with one P atom) or mixtures consisting of at least one chiral and at least one achiral monophosphorus compound are excellent ligand systems in the asymmetric Represent transition metal catalysis.
• These are fundamentally new processes in the field of enantioselective transition metal catalysis, in which known or new chiral mono-P compounds are used. It is also a structurally new type of chiral transition metal catalyst because two (or more) different monophosphorus compounds, of which at least one is a chiral monophosphorus compound, are bound to the metal.
• Such metal complexes have never been mentioned in the literature.
• phosphines As phosphines, phosphonites, phosphinites, phosphites or phosphoramidites, which are bound to the transition metals. As typical. Examples are rhodium, ruthenium or iridium complexes of optically active diphosphines such as BINAP (A. Miyashita, A. Yasuda, H. Takaya, K. Toriumi, T. Ito, T. Souchi, R. Noyori, J. Am. Chem. Soc, 102, 7932 (1980)), DuPHOS (MJ Burk, MF Gross, JP Martinez, J. Am. Chem. Soc, 117, 9375 (1995)), BICP (G. Zhu, P.
• diphosphines While most chiral phospho-containing ligands chelate diphosphorus compounds such as diphosphines (WS Knowles, Angew. Chem., 114, 2096 (2002); R. Noyori, Angew. Chem., 114, 2108 (2002)), diphosphites (e.g. BMT Reetz, T. Neugebauer, Angew. Chem., 111, 134 (1999)), diphosphinites (e.g. BR Selke, J. Organomet. Chem., 370, 249 (1989)) or diphosphonites (e.g. BMT Reetz, A Gosberg, R. Goddard, S.-H. Kyung, Chem. Commun.
• diphosphines WS Knowles, Angew. Chem., 114, 2096 (2002); R. Noyori, Angew. Chem., 114, 2108 (2002)
• diphosphites e.g. BMT Reetz, T. Neu
• the metal-ligand ratio is usually 1: 2.
• Some chiral monophosphines of the type R 1 R 2 R 3 P can also be good ligands in transition metal catalysis, although they are generally expensive (e.g. BWS Knowles , Angew. Chem., 114, 2096 (2002)).
• Monophosphorus-containing ligands of types I - III are particularly easily accessible and can be varied very easily due to the modular structure (I.V. Komarov, A. Börner, Angew. Chem., 113, 1237 (2001)).
• R in I, II or III By varying the radical R in I, II or III, a large number of chiral ligands can be built up, which enables ligand optimization for a given transition metal-catalyzed reaction (e.g. hydrogenation of a prochiral olefin, ketone or imine or hydroformylation of a prochiral olefin) is.
• transition metal-catalyzed reaction e.g. hydrogenation of a prochiral olefin, ketone or imine or hydroformylation of a prochiral olefin
• a central component of the present invention is the surprising finding that mixtures of two or more monophosphorus compounds, at least one of which is chiral, lead to higher enantioselectivities in transition metal-catalyzed substance conversions than in the previously customary procedure using a single structurally defined mono -P ligands.
• the transition metal catalysts we use, in which at least two different monophosphorus ligands (ie compounds with one P atom) are bonded to the metal, at least one monophosphorus ligand being chiral, are new. These catalysts can be used in a large number of different reaction types for the production of chiral organic compounds from prochiral organic compounds.
• the optically enriched or pure organic compounds are known to be renowned products or intermediate compounds in industry, for example in the manufacture of pharmaceuticals, crop protection agents and fragrances.
• the method can always work if at least two monophosphorus ligands (L) are bound to the metal (M) of the active catalyst ML X in the transition state of the reaction.
• L monophosphorus ligands
• M metal
• Such coordination relationships are known for metals from groups IIIb, IVb, Vb, Vlb, Vllb, Vlllb, Ib and llb and for the lanthanides and actinides. So come z. B.
• the increased enantioselectivity is always observed when the right mixture is chosen or the right choice of the R residues is made. This can be done quickly by e.g. B. combinations of different chiral phosphonites, e.g. B. Type I, tested as mixtures. More than two different chiral ligands, e.g. B. Type I, preferably two are used.
• mixtures of other chiral mono-P ligands can also be used.
• examples are mixtures of chiral monophosphites, eg. B. Type II, or mixtures of monophosphoramidites. z. B. Type III.
• chiral phosphines, phosphiranes, phosphinites, phosphoric acid tris and bis-amides, phosphoric acid mono- and diamides and phosphoric acid diester fluorides can also be used. just to name a few. In fact, any chiral connection with a P atom is possible. In practice there is an abundance of possible P ligands, the central framework of which is represented by the following formula IV.
• the atoms X, Y and Z can each be independently from the series carbon (C), nitrogen (N), oxygen (O), sulfur (S) or halogen (F, Cl, Br, I).
• X, Y and Z depending on their number of free valences, independently of each other further atoms or groups of atoms are bound, such as B. in the aforementioned Examples I, II and III.
• X, Y and Z can also be bridged to one another by the bonded atoms or groups of atoms, where X-P-Y can also be part of an aromatic system, in which case X is bound to P by a double bond and the substituent Z is omitted.
• substituents on IV may be mentioned by way of example:
• ligands IV have a modular structure, this means that the respective building blocks, for. B. chiral alcohols, chiral diols, chiral amines, chiral diamines or chiral amino alcohols are just to mention the most important possibilities. In the examples below, the absolute chirality is not shown in the drawing. It goes without saying that any ligand can be used in any possible configuration.
• the ligands are used in enantiomerically pure or enriched form. Enantiomerically pure ligands are preferably used.
• Typical examples of chiral ligands IVa are V and VI, which are central and axial chirality:
• Typical examples of chiral ligands IVb are VII and VIII:
• Typical examples of chiral ligands IVc are IX and X:
• Typical examples of chiral ligands IVd are the thio analogues of IX and X.
• Typical examples of chiral ligands IVe are XI and XII:
• Typical examples of chiral ligands IVf are VIII and XIV:
• R ' alkyl, aryl, sulfonyl
• R' alkyl, aryl, sulfonyl
• Typical examples of chiral ligands IVg and IVh are compounds I and the thio analogues.
• Typical examples of chiral ligands IVi are XV and XVI:
• R * alkyl, aryl, sulfonyl
• Typical examples of chiral ligands IVk are XIX and XX:
• R ' alkyl, aryl, sulfonyl
• R' alkyl, aryl, sulfonyl
• Typical examples of chiral ligands IVI are the thio analogues of XIV and XX.
• Typical examples of chiral ligands IVm are XXI and XXII:
• XXI F, Cl, Br or I
• XXII F, Cl, Br or I
• R alkyl, aryl, sulfonyl
• R alkyl, aryl, sulfonyl
• Typical examples of chiral ligands IVn and IVo are III and the thio analogues of III.
• Typical examples of chiral ligands IVp are XXIII and XXIV:
• R alkyl, aryl, sulfonyl
• R alkyl, aryl, sulfonyl
• Typical examples of chiral ligands IVg and IVs are II and the thio analogues of II.
• Typical examples of chiral ligands IVr are XXV and XXVI:
• the underlying principle of the invention does not only apply if the chiral P ligands belong to the same class of substances. An increase in enantioselectivity is also observed when the mixture of two (or more) chiral mono-P ligands belongs to different classes of P-compounds IV.
• a second variant of the invention also includes the mixture of two different P ligands, one containing (as previously described) chirality, the other being achiral.
• the use of a correct combination of a chiral ligand IV and an achiral analog IV leads surprisingly to a higher enantioselectivity in transition metal catalysis in such cases than when using the relevant chiral ligand alone. In some cases, such a combination can even be used to reverse the direction of enantioselectivity.
• SR Thi- ophosphite P
• the procedure known in the literature is used, which is usually used for the representation of traditional homocombinations M (L a ) n .
• metal complexes which carry ligands such as olefins, dienes, pyridine, CO or NO (to name just a few). The latter are completely or partially displaced by the reaction with the P ligands. Cationic metal complexes can also be used. Experts know a multitude of possibilities (G. Wiikinson, Comprehensive Coordination Chemistry, Pergamon Press, Oxford (1987); B. Corniis, WA Herrmann, Applied Homogeneous Catalysis with Organometallic Compounds, VCH, Weinheim (1996)).
• the metals include those of the groups Hlb, IVb, Vb, Vlb, VHb, VIII, lb and Hb of the periodic table as well as lanthanides and actinides.
• the 1 H, 3 C and 31 P NMR spectra of complex XXIX are characteristic of a "mixed" compound, ie they differ from the spectra of conventional complexes XXVII and XXVIII.
• Crucial to the invention is the unexpected finding that the entire catalytic profile of traditional catalysts, eg. B. XXVII and XXVIII, strongly from that of the "mixed" complex, e.g. B. JXXIX. It turns out that e.g. B. in an olefin hydrogenation, the catalyst XXIX according to the invention causes a significantly higher enantioselectivity than it is achieved using the traditional catalysts JXXVII and XXVIII. At the same time, a higher reaction rate is observed.
• traditional catalysts eg. B. XXVII and XXVIII
• the “mixed catalysts” according to the invention based on heterocombinations of different mono-P compounds can contain several chiral or achiral P ligands, preferably two different P ligands.
• the ratio of the P ligands can be varied relative to one another in the metal complex. Is it z. B. by two different ligands A and B, the relative ratio A: B can preferably be varied between 1: 4 and 4: 1, particularly preferably an A: B ratio of approximately 1: 1 is selected.
• the ratio of metal to substrate moves in the usual frame, d. H. between 1: 5 and 1: 1,000,000.
• Example 1 Rh-catalyzed hydrogenation of ⁇ / -Acylacryl Acidmethylester using ligands of type I, II and III.
• the conversion was determined by gas chromatography after dilution of the reaction solution.
• For the determination of the enantiomeric excess about 1.5 ml of the reaction solution was filtered adsorptively over a little silica gel and examined by gas chromatography or by means of HPLC. The experiments were carried out in parallel with 20 vessels.
• Rh / substrate ratio 1 1000; Rh / P ratio 1 2; Solvents: CH 2 CI 2 ; p (H 2 ): 1.3 bar; T: 20 ° C; Response time: 20 h; Turnover: 100%. Turnover: 1%.
• the conversion was determined by gas chromatography after dilution of the reaction solution.
• For the determination of the enantiomeric excess about 1.5 ml of the reaction solution was filtered adsorptively over a little silica gel and examined by gas chromatography or by means of HPLC. The experiments were carried out in parallel with 20 vessels.
• Example 3 Rh-catalyzed hydrogenation of 1- ⁇ / -acylaminostyrene using ligands of type I and II.
• Example 4 Rh-catalyzed hydrogenation of 1- ⁇ / -acylamino-1-p-chlorophenylethylene.
• Example 5 Variation of the ratio of the two P ligands Ia and Id in the Rh-catalyzed hydrogenation of 1- / V-acylaminostyrene.
• Rh / ((R) la / (R) ld) ratio was 1: 2 and the Rh / substrate ratio 1: 500.
• Example e Rh-catalyzed hydrogenation of 1- ⁇ / -acylamino-1-naphthylethylene using type I ligands.
• Example 7 Rh-catalyzed hydrogenation of dimethyl itaconic ester using ligands of type I.
• Rh / P ratio was 1: 2 and the Rh / substrate ratio was 1: 1000.
• Solvent CH 2 CI 2 ; p (H 2 ): 1.3 bar; T: 20 ° C; Response time: 20 h; Turnover: 100% ..
• the quantitative hydrogenation can also be carried out by reducing the Rh / substrate ratio under otherwise identical conditions.
• Rh: substrate 1: 6000 the ee value is 95.8% (R); at 1: 10,000 the ee value is 95.4% (R); at 1: 20,000 the ee value is 94.6% (R).
• Example 8 Rh-catalyzed hydrogenation of ⁇ / -acylaminoacrylic acid methyl ester using chiral phosphonites I, phosphites II, phosphoramidites III and achiral mono-P ligands.
• Rh / substrate ratio 1 1000; Rh / P ratio 1: 2; Solvents: CH 2 CI 2 ; p (H 2 ): 1.3 bar; T: 20 ° C; Response time: 20 h; Turnover: 100%.
• Example 9 Preparation and characterization of the catalyst system Rh [Ia] [ld] [COD] BF 4 + Rh [la] 2 [COD] BF 4 + Rh [ld] 2 [COD] BF 4 .
• Example 10 Preparation, isolation and characterization of the catalyst system Rh [la] [Id] [COD] BF 4 + Rh [la] 2 [COD] BF 4 + Rh [ld] 2 [COD] BF 4 using ESI-MS.
• Example 11 Examination of a mixture of Rh [la] 2 [COD] BF 4 and Rh [ld] 2 [COD] BF 4
• Rh [la] 2 [COD] BF 4 (3.3 mg; 0.0034 mmol; 0.5 ml CD 2 CI 2 ) and a solution of Rh [Id] 2 [COD] BF (3.5 mg; 0.0034 mmol; 0.5 ml CD 2 CI 2 ) were mixed.
• the mixture was examined by 31 P NMR spectroscopy. It can be seen from the signals (analogous to Example 9) that the same components Rh [(R) Ia] 2 [COD] BF 4 (XXVII), Rh [(R) Id] 2 [COD] BF 4 (XXVIII) and Rh [(R) la] [(R)! D] BF 4 (XXIX) as in Example 9.
• Example 12 Preparation, isolation and characterization of the catalyst system Rh [la] [lc] [COD] BF 4 + Rh [Ia] 2 [COD] BF 4 + Rh [lc] 2 [COD] BF 4 by means of ESI-MS.
• Example 13 Preparation, isolation and characterization of the catalyst system Rh [Ila] [Ic] [COD] BF 4 + Rh [IIa] 2 [COD] BF 4 + Rh [Ic] 2 [COD] BF 4 using ESI-MS.

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