WO2022128833A1 - Complexes métal-ligand de transition solide - Google Patents

Complexes métal-ligand de transition solide Download PDF

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Publication number
WO2022128833A1
WO2022128833A1 PCT/EP2021/085343 EP2021085343W WO2022128833A1 WO 2022128833 A1 WO2022128833 A1 WO 2022128833A1 EP 2021085343 W EP2021085343 W EP 2021085343W WO 2022128833 A1 WO2022128833 A1 WO 2022128833A1
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WO
WIPO (PCT)
Prior art keywords
sulfonic acid
transition metal
propane
butylphosphino
ligand
Prior art date
Application number
PCT/EP2021/085343
Other languages
English (en)
Inventor
Steffen Kress
Mike Brandner
Ralf Knierieme
Original Assignee
Merck Patent Gmbh
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Publication date
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Publication of WO2022128833A1 publication Critical patent/WO2022128833A1/fr

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    • 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
    • C07F15/006—Palladium compounds
    • C07F15/0066—Palladium compounds without a metal-carbon linkage
    • 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
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • 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
    • B01J31/24—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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/827—Iridium
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/828—Platinum
    • 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
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/30—Non-coordinating groups comprising sulfur
    • B01J2540/32—Sulfonic acid groups or their salts

Definitions

  • the present invention refers to the area of organic synthesis and concerns certain transition metal-ligand complexes, a process for their manufacture, heterogeneous catalysts comprising said complexes and their use in specific organic reactions.
  • Transition metal complexes are indispensable in homogeneous catalysis.
  • the central metal atom is complexed by ligands, which can strongly influence selectivity and conversion.
  • the homogeneous transition metal complex is modified by adding special, mostly water-soluble ligands and converted into an aqueous phase.
  • Homogeneous catalysts have also reached the large-scale industry in recent decades: In a process variant of hydroformylation, for example, the Ruhrchemie Rhone-Poulenc process, reaction is mediated by a rhodium- triphenylphosphane trisulfonate complex (“TPPTS”). Due to the sulfonated ligand, the catalyst remains in the aqueous phase, while the product of the process, n-butanal produced from propene, hydrogen and carbon monoxide, forms an organic phase.
  • TPTS rhodium- triphenylphosphane trisulfonate complex
  • transition metals such as palladium, platinum or rhodium are combined with sulfonate phosphane ligands.
  • the zwitterionic ligand 3-(di-tert- butylphosphino)propane-1 -sulfonate (“DTBPPS”) is used in many palladium-catalyzed reactions, such as Suzuki coupling or Suzuki-Miyaura reaction for the synthesis of biphenyls or biphenyl derivatives by forming a C-C bond.
  • DTBPPS zwitterionic ligand 3-(di-tert- butylphosphino)propane-1 -sulfonate
  • Suzuki coupling or Suzuki-Miyaura reaction for the synthesis of biphenyls or biphenyl derivatives by forming a C-C bond.
  • Sonogashira reaction for coupling of terminal alkynes with aryl or vinyl halides under palladium-copper catalysis and using an
  • the catalytic active species is formed prior to the reaction by mixing a suitable transition metal precursor and DTBPPS in water or mixtures of water with organic solvents.
  • the transition metal-ligand complex is prepared in-situ and directly added to the reaction mixture.
  • DTBPPS 3-(di-tert-butylphosphino)propane-1 -sulfonate
  • ASTRA ZENECA The use of 3-(di-tert-butylphosphino)propane-1 -sulfonate (DTBPPS) in catalysts, for example for the preparation of imidazo[4,5-C]quinoline-2-one compounds for cancer therapy, is known from the publications WO 2017 076895 A1, WO 2017 153578 A1 and WO 2018 167203 A1 (ASTRA ZENECA).
  • the catalyst is prepared in-situ and added directly to the reaction mixture as a solution.
  • Fig. 1 Calculated powdered X-ray diffraction pattern for [Pd(DTBPPS)Cl2]2 prepared in Example 1.
  • Fig. 2 3D plot according to the X-ray structure solution for [Pd(DTBPPS)Cl2]2 prepared as disodium salt in Example 1.
  • Fig. 3a and 3b 3D plots (different perspectives) according to the X-ray structure solution for [Pd(DTBPPS)Cl2]2 prepared as disodium salt in Example 1 .
  • a first object of the present invention refers to a solid transition metal-ligand complex of formula (I) in which M1 and M2 individually stand for a transition metal selected from the group consisting of palladium, platinum, rhodium, and iridium;
  • Hal represents chlorine, bromine or iodine
  • R1 , R2, R3 and R4 individually stand for linear or branched alkyl groups having 1 to 12 and preferably 2 to 10 and more preferably 3 to 6 carbon atoms, or cycloalkyl or aryl groups having 3 to 12 and preferably 5 to 12 and most preferably 6 to 10 carbon atoms, including phenyl, adamantyl and norbornyl groups; and L1 and L2 individually stand for a -(A)-(Z) group in which A represents a linear or branched alkylene group having 1 to 6 carbon atoms and Z stands for a -SO3H group or its alkaline or alkaline- earth salt.
  • the complexes may include 1 , 2, 3, 4, 5 or more molecules hydrate water.
  • the complex is represented by the following solid transition metal-ligand complex of formula (II):
  • Another object of the present invention refers to a method for manufacturing the solid transition metal-ligand complexes of formula (I) or (II) comprising or consisting of the following steps: (a) providing a transition metal halide according to formula (Illa) to (Hid) or a mixture thereof:
  • step (c) blending the ligand solution of step (b) with the transition metal halide of step (a) to form a suspension;
  • the preferred halide is palladium dichloride.
  • the preferred ligand is 3-(di-tert- butylphosphino)propane-1 -sulfonic acid or its sodium salt.
  • said source of alkali can be an aqueous solution of an alkali hydroxide, an alkali carbonate or alkali hydrogen carbonate.
  • Suitable examples encompass aqueous solutions of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, and mixtures thereof.
  • Particularly preferred is, however, an aqueous solution of sodium hydrogen carbonate, since this source of alkali, particularly when added dropwise, generates only little gas in small bubbles and supports a fast and complete precipitation.
  • the reaction is conducted at a temperature of from about 30 to about 80 °C, and preferably at about 50 °C.
  • the precipitated crystals are preferably cooled to about 0 °C, separated off from the aqueous phase by filtration, and dried to constant weight for example in a desiccator.
  • the crystals can be stored for at least 6 weeks in the dark, preferably under inert gas.
  • Another object of the present invention refers to a heterogeneous catalyst comprising or consisting of:
  • Suitable supports can be selected for example from the group consisting of activated charcoal, alumina oxide, silica dioxide, alkaline or alkaline earth silicates or mixtures thereof.
  • the loading can range from about 0.1 to about 5 wt. -percent, preferably from about 0.5 to about 2 wt. -percent.
  • Another object of the present invention encompasses a method for manufacturing said heterogeneous catalysts comprising or consisting of the following steps:
  • step (iii) bringing the aqueous solution of step (i) into contact with the support of step(ii) and precipitate the solid complex on the surface of the support;
  • Another object of the present invention refers to the use of the solid transition metal-ligand complexes or the heterogeneous catalysts as described above as catalysts, preferably for cross-coupling reactions such as Suzuki couplings and Sonogashira reactions.
  • the comparative example was conducted according to WO 2018 167203 A1 .
  • Degassed water (30 mL) was added to sodium tetrachloropalladate(ll) (0.41 g, 1.39 mmol) and 3-(di-tert-butylphosphino)propane-1 -sulfonic acid (0.75 g, 2.79 mmol) at ambient temperature under an inert atmosphere.
  • the suspension was stirred for 5 minutes, then the solid removed by filtration and discarded to leave the desired reagent as a red-brownish solution, which was ready for subsequent addition as a catalyst to a reaction mixture
  • Example 1 The following examples were made for comparing the activities of the solid catalyst according to the present invention (Example 1 ) and the in-situ catalyst according to the state of the art (Comparative Example C1 ). Both catalysts were tested in an aqueous phase Suzuki coupling of aryl bromides [see W.S. BROWN et al. in SYNTHESIS, 12, p 1965-1970 (2008)]. The results are shown in Table 1 .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un complexe métal-ligand de transition solide pouvant être obtenu par ajout d'une source d'alcali à une suspension aqueuse d'halogénures de métaux de transition et de ligands appropriés.
PCT/EP2021/085343 2020-12-15 2021-12-13 Complexes métal-ligand de transition solide WO2022128833A1 (fr)

Applications Claiming Priority (2)

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EP20214232.9 2020-12-15
EP20214232 2020-12-15

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017076895A1 (fr) 2015-11-03 2017-05-11 Astrazeneca Ab Composés imidazo[4,5-c]quinoléine-2-one et leur utilisation dans le traitement du cancer
WO2017153578A1 (fr) 2016-03-11 2017-09-14 Astrazeneca Ab Composés imidazo[4,5-c]quinolin-2-one et leur utilisation pour traiter le cancer
WO2018167203A1 (fr) 2017-03-16 2018-09-20 Astrazeneca Ab Composés imidazo[4,5-c]quinolin-2-one deutérés et leur utilisation dans le traitement du cancer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017076895A1 (fr) 2015-11-03 2017-05-11 Astrazeneca Ab Composés imidazo[4,5-c]quinoléine-2-one et leur utilisation dans le traitement du cancer
WO2017153578A1 (fr) 2016-03-11 2017-09-14 Astrazeneca Ab Composés imidazo[4,5-c]quinolin-2-one et leur utilisation pour traiter le cancer
WO2018167203A1 (fr) 2017-03-16 2018-09-20 Astrazeneca Ab Composés imidazo[4,5-c]quinolin-2-one deutérés et leur utilisation dans le traitement du cancer

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
BROWN W S ET AL: "Sterically demanding, zwitterionic trialkylphosphonium sulfonates as air-stable ligand precursors for efficient palladium-catalyzed cross-couplings of aryl bromides and chlorides", SYNTHESIS, GEORG THIEME VERLAG, STUTTGART, DE, no. 12, 16 May 2008 (2008-05-16), pages 1965 - 1970, XP002556845, ISSN: 0039-7881, DOI: 10.1055/S-2008-1067095 *
PAETZOLD E ET AL: "Suzuki reactions in aqueous multi-phase systems promoted by supported detergents", JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL, ELSEVIER, AMSTERDAM, NL, vol. 214, no. 2, 1 June 2004 (2004-06-01), pages 241 - 247, XP009147114, ISSN: 1381-1169, [retrieved on 20040213], DOI: 10.1016/J.MOLCATA.2003.12.02 *
W.S. BROWN ET AL., SYNTHESIS, vol. 12, 2008, pages 1965 - 1970
WEDGWOOD J L ET AL: "Water soluble platinum(II) and palladium(II) complexes of alkyl sulfonated phosphines", INORGANICA CHIMICA ACTA, ELSEVIER BV, NL, vol. 290, no. 2, 15 July 1999 (1999-07-15), pages 189 - 196, XP027217591, ISSN: 0020-1693, [retrieved on 19990715] *
WEDGWOOD J L: "Water soluble platinum(II) and palladium(II) complexes of alkyl sulfonated phosphines", INORGANICA CHIMICA ACTA, vol. 290, no. 2, 1 January 1999 (1999-01-01), pages 189 - 196, XP055892848 *

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