EP4688797A2 - Catalyseur d'hydroformylation supramoléculaire - Google Patents

Catalyseur d'hydroformylation supramoléculaire

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Publication number
EP4688797A2
EP4688797A2 EP24715729.0A EP24715729A EP4688797A2 EP 4688797 A2 EP4688797 A2 EP 4688797A2 EP 24715729 A EP24715729 A EP 24715729A EP 4688797 A2 EP4688797 A2 EP 4688797A2
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European Patent Office
Prior art keywords
branched
linear
alkyl
solution
formula
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EP24715729.0A
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German (de)
English (en)
Inventor
Anton VIDAL FERRAN
Andrés ROMERO NAVARRO
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Universitat de Barcelona UB
Institut Catala dInvestigacio Quimica ICIQ
Institucio Catalana de Recerca i Estudis Avancats ICREA
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Universitat de Barcelona UB
Institut Catala dInvestigacio Quimica ICIQ
Institucio Catalana de Recerca i Estudis Avancats ICREA
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Publication of EP4688797A2 publication Critical patent/EP4688797A2/fr
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—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
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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
    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
    • B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
    • B01J31/1683—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins the linkage being to a soluble polymer, e.g. PEG or dendrimer, i.e. molecular weight enlarged complexes
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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
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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
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
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    • 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
    • C07D317/10—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 not condensed with other rings
    • C07D317/14—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 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D317/26—Radicals substituted by doubly bound oxygen or sulfur atoms or by two such atoms singly bound to the same carbon atom
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    • 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
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0202—Polynuclearity
    • B01J2531/0205—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
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    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0286—Complexes comprising ligands or other components characterized by their function
    • B01J2531/0297—Non-coordinating anions
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/11—Lithium
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/12—Sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/13—Potassium
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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    • B01J2531/14—Rubidium
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/20—Non-coordinating groups comprising halogens
    • B01J2540/22—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate

Definitions

  • the present invention relates to the field of catalysts used in hydroformylation reactions.
  • the hydroformylation reaction also known as oxo process, is an industrial process for the production of aldehydes from alkenes.lt consists in the addition of a formyl group (CHO) and a hydrogen atom to a carbon-carbon double bond. This reaction is important because aldehydes may be converted into secondary products in an easy way.
  • CHO formyl group
  • This process is usually carried out with high pressures (between 10 and 100 atmospheres) of carbon monoxide and hydrogen, at temperatures between 40 °C and 200 °C, in the presence of transition metal catalysts.
  • Cobalt catalysts are used in the industrial processes known as BASF-oxo process, Exxon process, and Shell process, whereas rhodium catalysts are used in Union Carbide process, and Ruhrchemie/Rhone-Poulenc process.
  • R-CH CH 2 - ⁇ R-CH 2 -CH 2 -CHO + R-CH-CH3
  • Rhodium catalysts providing preferably linear aldehydes are disclosed in, for example, Cuny et al., Practical high yield, regioselective, rhodium-catalyzed hydroformylation of functionalized a-olefins, J. Am. Chem.
  • An aspect of the present invention relates to a hydroformylation catalyst. Another aspect of the invention relates to a ligand.
  • Another aspect of the invention relates to a process for preparing the ligand.
  • Another aspect of the invention relates to a process for preparing the catalyst.
  • Another aspect of the invention relates tothe use of thecatalyst in a hydroformylation reaction.
  • Another aspect of the invention is a process for preparing aldehydes by a hydroformylation reaction.
  • the present invention relates to a hydroformylation catalystof formula (I) comprising a rhodium carbonyl hydride [Rh], a ligand L and, optionally, a regulation agent [RA], wherein
  • Rh is Rh(CO) x (H), wherein x is 1 or 2, preferably x is 2;
  • [RA] is a regulation agent selected from a salt of formula M + A , wherein M + is selected from an alkali metal cation and ammonium, and A is a non-coordinating anion; the ligand Lhas formula (II)
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from linear or branched C1-C5 alkyl, linear or branched C1-C5 halogenated alkyl, linear or branched O-(Ci-C 5 )-alkyl, linear or branched N-(Ci-C 5 )-alkyl, linear or branched (Ci-C 8 )-P e rfl uo rc>alkyl, linear or branched O-(Ci-C 8 )-P e rfl uo r°alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl; preferably selected fromlinear or branched C1-C5 alkyl, linear or branched O-(Ci-C 5 )- alkyl, linear or branched O-(Ci
  • p, q, r and s are independently selected from land 2; t is selected from 0 and 1 ; and u and v are independently selected from 1 , 2, 3 and 4.
  • the inventors of the present invention have developed new hydroformylation catalysts, which surprisingly show regioselective activity yielding selective formation of terminal aldehydes in front of branched aldehydes in combination with high conversion yields.
  • the combination of a regulation agent, when t 1 , with a metal precursor with conformationally transformable ligands, which incorporate a polyether chain as the regulation site, behave as supramolecularly regulated catalysts.
  • Said catalysts are assembled by means of multiple weak intramolecular interactions to perform supramolecular catalysis.
  • supramolecular regulation of the catalytic site is a useful approach in catalysis.
  • RA regulation agent
  • This strategy seeks to override one of the intrinsic limitations of catalysts: their lack of generality. It is well known in the field that structural changes in the substrate(s) often translate into a loss of selectivity, with structural variation of the catalytic system being required for improving the outcome of the reaction for the new substrate.
  • Supramolecular regulation is an efficient strategy to produce libraries of catalysts, whose members preserve the main structural characteristics of the whole set of catalysts, but incorporate subtle structural differences at the catalytic site that are related to the regulation agent used. Overall, one of the members a particular library of catalysts is capable of adapting to the requirements of a given substrate, providing the highest performance in terms of regioselectivity for this particular substrate. Adapting the covalent backbone of a catalyst to increase their substrate scope faces significant synthetic hurdles.
  • the hydroformylation catalyst of the present invention comprises three differentiated parts: a rhodium carbonyl hydride[Rh], a ligand, and optionally a regulation agent [RA],
  • a rhodium carbonyl hydride[Rh] a ligand
  • RA regulation agent
  • the equivalent ratio of [Rh]:[RA]:ligand is usually comprised between 1 :1 :1 and 1 :2: 1.2, preferably between 1 : 1.1 :1 and 1 :1.4: 1.1 , and more preferably between 1 :1.25:1.1 and 1 :1.35:1.1.
  • Rh representsthe complex Rh(CO) x (H), whereinx is 1 or 2, and preferably x is 2.
  • [RA] is a regulation agent selected a salt of formula M + A , wherein M + is selected from an alkali metal cation and ammonium, and A is a non-coordinating anion; preferably M + is an alkali metal cation, and yet more preferably M + is selected from Li + , Na + , K + , Rb + , and Cs + .
  • the non-coordinating anion A is preferably selected from BF 4 , PF 6 , CF 3 COO or [B(3,5-(CF 3 ) 2 C 6 H 3 ) 4 ] (abbreviated as BArF), and more preferably is[B(3,5-(CF 3 ) 2 C 6 H 3 ) 4 ] (BArF).
  • Another aspect of the invention is a ligand that is comprised in the structure of the hydroformylation catalyst of the invention, defined according to general formula (II) above.
  • the ligand is according to general formula (II), wherein R 1 , R 2 , R 3 and R 4 are t-Bu, and p, q, r and s are 2, and R 1 , R 2 , R 3 and R 4 are in positions 3, 5, 3’ and 5’ of the biphenyl rings, 0 ⁇ m ⁇ 5 and 0 ⁇ n ⁇ 5 and n+m > 1 , and , , the meaning as above, in a preferred embodiment u and v are 0.
  • the ligand is according to general formula (II), wherein R 1 , R 2 , R 3 and R 4 are t-Bu, and p, q, r and s are 2, and R 1 , R 2 , R 3 and R 4 are in positions 3, 5, 3’ and 5’ of the biphenyl rings, 0 ⁇ m ⁇ 5 and 0 ⁇ n ⁇ 5 and n+m > 1 , and X is oxygen.
  • n+m is selected from 2, 3, 4, 5, 6, 7, 8, 9 and 10; in a preferred embodiment n+m is an integer from 2to 5. In a preferred embodiment n+m is 2, in another preferred embodiment n+m is 5.
  • the ligand is defined according to formula (Ila):
  • the ligand when n+m is 5, the ligand is defined according to formula (lib):
  • the ligand is according to general formula (II), wherein R 1 , R 2 , R 3 and R 4 are t-Bu, and p, g, r and s are 2, and R 1 , R 2 , R 3 and R 4 are in positions 3, 5, 3’ and 5’ of the biphenyl rings, 0 ⁇ m ⁇ 5 and 0 ⁇ n ⁇ 5 and n+m > 1 , and wherein R 5 , R 6 , u and v have the meaning as above.
  • the ligand is selected from compound defined by formula (Ila), (lib) and (lie). In a more preferred embodiment, the ligand is compound defined by formula (Ila).
  • ligand of formula (Ila) is designated as ligand L1
  • ligand of formula (He) is designated as ligand L2
  • ligand of formula (lib) is designated as ligand L3.
  • Another aspect of the invention is a process for preparing the ligand of formula (II).
  • the process for preparing the ligand of formula (II) comprises the reaction between compound of formula (Illa) or a combination of compounds of formula (Illa) and (lllb): with compound of formula (IV)
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from linear or branched C1-C5 alkyl, linear or branched C1-C5 halogenated alkyl, linear or branched O-(Ci-C 5 )-alkyl, linear or branched N-(Ci-C 5 )-alkyl, linear or branched (Ci-C 8 )-P e rfl uo rc>alkyl, linear or branched O-(Ci-C 8 )-P e rfl uo r°alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl; preferably selected fromlinear or branched C1-C5 alkyl, linear or branched O-(Ci-C 5 )- alkyl, linear or branched O-(Ci
  • Compounds of formula (Illa) and (I I lb) may be prepared according to a known process, such as disclosed, for example, in US4769498, wherein phosphorus trichloride (PCI 3 ) is reacted with a substituted 1 ,1’-biphenyl-2,2’-diol compound.
  • PCI 3 phosphorus trichloride
  • symmetrical polyphosphite ligands i.e., using only compound of formula (Illa) can be prepared by adding the diol (compound of formula IV) and chlorophosphite (compound of formula (Illa)) in either order.
  • compound of formula (IV) is added slowly at a temperature comprised between 0 °C and 30 °C, preferably between 0 °C and 25 °C, and more preferably about 20 °C, to compound of formula (Illa) in the presence of the organic base, preferably triethylamine.
  • the molar ratio of compound of formula (IV) to compound of formula (Illa) and to the organicbase is comprised between 1:2:2 and 1:5:5, preferably between 1 :2:2.2 and 1:3:4, and more preferably between 1:2.1 :2.3 and 1:2.2:2.4.
  • Asymmetrical polyphosphite ligands may be prepared in analogous way using a combination of compounds of formula (Ila) and (lllb).
  • Ligands of formula (II) in solid form may be easily separated from the reaction solution, recovered, and purified if desired, in any conventional manner employing standard techniques well-known by the skilled person in the field of organic synthesis, such as, for example, evaporation, recrystallization, chromatographic purification and/or filtration.
  • Another aspect of the invention is a process for preparing said catalyst.
  • the synthetic strategies are summarized in Scheme I: Scheme I
  • Rh catalysts for hydroformylations [Rh(CO) 2 )(H)(L «RA)J or [Rh(CO) 2 )(H)(L)]
  • They can be directly used from the prepared solutions, or they can be isolated as solids. These solids are stable for a few days if stored at low temperature (/.e., below 0 °C) under a CO atmosphere.
  • the process for preparing the catalyst of the invention comprises any one of the following alternatives a), b) or c): a) la)preparing a solution of a ligand (L), a regulation agent (RA), if present, and a rhodium (l)complex, in an inert solvent, and
  • step 2a) pressurizing the solution of step 1a) in an autoclave with a combination of H 2 /CO; b) lb) preparing a solution of a ligand (L) and a regulation agent (RA) in an inert solvent, and
  • step 2b) pressurizing the solution of step 2b) in an autoclave with a combination of H 2 /CO;
  • step 1c) preparing a solution of a ligand (L), and a rhodium (I) complexin an inert solvent, 2c) pressurizing the solution of step 1c) in an autoclave with a combination of
  • step 3c) adding a regulation agent to the solution obtained in step 2c) under a pressure of H 2 /CO.
  • the alternative a) represents an in situ preparation of the hydroformylation catalyst, whereas b) and c) represent two alternatives of the step-wise preparation of said catalyst.
  • Rhodium (I) complexes suitable in the process of the invention are any rhodium (l)complex, which is preferably selected from [Rh(K 2 O,O’-acac)(CO) 2 ], [Rh(K 2 O,O’- ⁇ 2- ethylhexanoate ⁇ ) 3 ], [Rh(K 2 O,O’-acac)(r
  • the preparation in situ of the hydroformylation catalyst of the invention may be carried out by preparing a solution of a ligand (L), a regulation agent (RA), if present, and a rhodium (I) complex, as disclosed above, in an inert solvent, for example, selected from toluene, THF and mixtures thereof, and transferring said solution to an autoclave reactor, which is pressurized at a pressure comprised between 1bar (10 5 Pa) and 20 bar(2x10 6 Pa), preferably about 10 bar (10 6 Pa) of H 2 /CO in a ratio comprised between 1 :10 and 10:1 , preferably between 3:7 and 7:3, and more preferably 1 :1, and heated at a temperature comprised between 50°C and 120 °C, preferably between 60 °C and 100 °C.
  • an inert solvent for example, selected from toluene, THF and mixtures thereof
  • the mixture is stirred for a period of time comprised between 12 h and 24 h, preferably about 18 h. After that time, the reactor is cooled usually to room temperature, depressurized in a well-ventilated fume hood.
  • the reaction mixture comprising the catalyst of formula [Rh(CO) 2 )(H)(L*RA)], is ready to be used for hydroformylations.
  • the solvent can also be removed in vacuo to dryness, obtaining a solid, which is stable if stored at low temperature (below 0 °C) under CO atmosphere.
  • the hydroformylation catalyst of the invention is prepared following the middle route in Scheme I, wherein, in a first step, a solution of a ligand (L) and a regulation agent (RA) in an inert solvent, for example, selected from toluene, THF and mixtures thereof, is stirred for a period of time of about 1 h.
  • a solution of a ligand (L) and a regulation agent (RA) in an inert solvent for example, selected from toluene, THF and mixtures thereof.
  • RA regulation agent
  • the reaction mixture is ready to be used in the next synthetic step, if desired, alternatively, the solvent may also be removed in vacuo to dryness, obtaining a solid (L*RA), which is stable if stored at low temperature (below 0 °C) under a N 2 atmosphere.
  • the reaction mixture of the previous step comprising L*RAis transferred to an autoclave reactor, which is pressurized at a pressure comprised between 1 bar (10 5 Pa) and 20 bar (2x10 6 Pa), preferably about 10 bar (10 6 Pa) of H 2 /CO in a ratio comprised between 1 :10 and 10:1 , preferably between 3:7 and 7:3, and more preferably 1 :1 , and heated at a temperature comprised between 50°C and 120 °C, preferably between 60 °C and 100 °C.
  • the mixture is stirred for a period of time comprised between 12 h and 24 h, preferably about 18 h.
  • the reactor is cooled usually to room temperature, depressurized in a well-ventilated fume hood, and the catalyst of formula [Rh(CO) 2 )(H)(L*RA)] is ready to be used for hydroformylations.
  • the hydroformylation catalyst of the invention is prepared following the bottom route in Scheme I, wherein, in a first step a solution of ligand L and a rhodium (I) complex, as disclosed above, in an inert solvent, for example, selected from toluene, THF and mixtures thereof, is transferred to an autoclave reactor, which is pressurized at a pressure comprised between 1 bar (10 5 Pa) and 20 bar (2x10 6 Pa), preferably about 10 bar (10 6 Pa) of H 2 /CO in a ratio comprised between 1 :10 and 10:1 , preferably between 3:7 and 7:3, and more preferably 1 :1 , and heated at a temperature comprised between 50°C and 120 °C, preferably between 60 °C and 100 °C.
  • a solution of ligand L and a rhodium (I) complex as disclosed above, in an inert solvent, for example, selected from toluene, THF and mixtures thereof, is transferred to an autoclave
  • the mixture is stirred for a period of time comprised between 12 h and 24 h, preferably about 18 h.
  • the reactor was cooled to room temperature, depressurized in a well-ventilated fume hood and the reaction mixture, comprising a hydroformylation catalyst of formula [Rh(CO) 2 (H)(L)], was ready to be used for hydroformylations, if desired.
  • the solvent can also be removed in vacuo to dryness.
  • the resulting solid is stable if stored at low temperature (below 0 °C) under a CO atmosphere.
  • a regulation agent may be added as a solid onto a solution of [Rh(CO) 2 (H)(L)], as prepared in the first step, under a pressure comprised between 1 bar (10 5 Pa) and 2 bar (2x10 5 Pa), preferably aboutl bar (10 5 Pa) of H 2 /CO in a ratio comprised between 1 :10 and 10:1 , preferably between 3:7 and 7:3, and more preferably 1 :1 ,
  • the mixture was allowed to stir under CO atmosphere for 1 hour, obtaining a hydroformylation catalyst of formula [Rh(CO) 2 )(H)(L*RA)].
  • Another aspect of the invention is use of the catalyst of the invention in hydroformylation reactions.
  • hydroformylation catalysts of the invention surprisingly show regioselective activity yielding selective formation of terminal aldehydes in front of branched aldehydes in combination with high conversion yields.
  • Final regioselectivities (/.e., branched to linear ratio, abbreviated as b/l ratio) up to 2:98 in favor of the linear aldehydes are obtained with the ligand L1of formula (lla)and in the presence of a regulation agent.
  • the pressure of the reaction can be reduced to atmospheric pressure without loss of activity and regioselectivity, which makes these catalysts attractive for future industrial applications.
  • a main advantage of the hydroformylation catalyst of the invention is that while typical catalyst optimization towards the linear aldehyde for a substrate(s) relies on designing, synthesizing and testing new types of catalysts with structural variations on the catalyst via covalent chemistry being necessary to encompass the different types of olefins, the present invention is based on the use of the same ligand with structurally diverse external agents (/.e., regulation agents, RA) that modify the outcome of the reaction.
  • the main advantage is the ease of synthesis of the whole library of catalysts (just by mixing the same ligand with an array of RAs and allowing the resulting mixtures to evolve to the catalysts) compared to covalently synthesizing a different “lead catalyst” for each substrate.
  • the hydroformylation reaction comprises any one of the following alternatives a) or b): a)
  • step 2a) pressurizing the solution of step 1a) in an autoclave with a combination of
  • step 2b) pressurizing the solution of step 1 b) in an autoclave with a combination of H 2 /CO.
  • RA is a regulation agent as defined above, and the preferred embodiments of the rhodium (I) complex are defined above.
  • the hydroformylation reaction takes place usually in an inert solvent, for example, selected from toluene, THF and mixtures thereof.
  • Pressurization of the solution comprising the catalyst and the olefin (substrate to hydroformylate) is generally carried out in an autoclave reactor, wherein the pressure is usually comprised between 1 bar (10 5 Pa) and 80 bar (8x10 6 Pa), preferably about 10 bar (10 6 Pa) of H 2 /CO in a ratio comprised between 1 :10 and 10:1 , preferably between 3:7 and 7:3, and more preferably 1 :1 , and heated at a temperature comprised between 25°C and 120 °C, preferably between 35 °C and 100 °C The mixture is stirred for a period of time comprised between 12 h and 24 h, preferably about 18 h. After that time, the reactor is cooled usually to room temperature, depressurized in a well-ventilated fume hood.
  • Conversion, chemo- and regioselectivity of the products arising from hydroformylation reaction conditions may be determined by GC analysis on an achiral stationary phase (HP-5) using dodecane as the internal standard.
  • Another aspect of the invention is a process for preparing aldehydes by a hydroformylation reaction, which comprises the reaction of an olefin with a combination of H 2 /CO in the presence of a catalyst according to the invention.
  • a hydroformylation catalyst of formula (I) comprising a rhodium carbonyl hydride [Rh], a ligand Land, optionally, a regulation agent [RA]; wherein
  • Rh is Rh(CO) x H, wherein x is 1 or 2, preferably x is 2;
  • [RA] is a regulation agent of formula M + A , wherein M + is selected from an alkali metal cation and ammonium, and A is a non-coordinating anion; , , , , independently selected from linear or branched C1-C5 alkyl, linear or branched C1-C5 halogenated alkyl, linear or branched O-(Ci-C 5 )-alkyl, linear or branched N-(Ci-C 5 )-alkyl, linear or branched (Ci-C 8 )-perfluoroalkyl, linear or branched O-(Ci-C 8 )-perfluoroalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl; preferably selected fromlinear or branched C1-C5 alkyl, linear or branched O-(Ci-C 5 )- al
  • p, q, r and s are independently selected from 1 and 2; t is selected from 0 and 1 ; and u and v are independently selected from 1 , 2, 3 and 4.
  • R 1 , R 2 , R 3 and R 4 are t-Bu; p, q, r and s are 2 ; R 1 , R 2 , R 3 and R 4 are in positions 3, 5, 3’ and 5’ of the biphenyl rings; 0 ⁇ m ⁇ 5 ; 0 ⁇ n ⁇ 5 ; n+m > 1 ; and wherein R 5 , R 6 , u and v have the meaning as above. In a preferred embodiment u and v are 0.
  • n+m is an integer from 2 to 5.
  • a process for preparing the catalyst of formula (I) comprising any one of the following alternatives a), b) or c): a) la) preparing a solution of a ligand L, a regulation agent (RA), if present, and a rhodium (I) complex, in an inert solvent, and
  • step 2a) pressurizing the solution of step 1a) in an autoclave with a combination of H 2 /CO; b) l b) preparing a solution of a ligand Land a regulation agent (RA) in an inert solvent, and
  • step 3c) adding a regulation agent to the solution obtained in step 2c) under a pressure of H 2 /CO.
  • hydroformylation reaction comprises any one of the following alternatives a) or b): a) la) preparing a solution of a ligand Ldefined by formula (II), a regulation agent (RA), a Rh complex, and an olefin in an inert solvent, and
  • step 2a) pressurizing the solution of step 1a) in an autoclave with a combination of H 2 /CO; b) l b) adding an olefin to the hydroformylation catalyst prepared in situ defined by any one of the formulas [Rh(CO) 2 (H)(L)]or [Rh(CO) 2 (H)(L «RA)J, and
  • step 2b) pressurizing the solution of step 1 b) in an autoclave with a combination of H 2 /CO, wherein the ligand Lis according to any one of embodiments 14 to 21 , the regulation agent RA is as defined in any one of embodiments4 and 5, and the Rh complex is as defined in embodiment 15. wherein
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from linear or branched C1-C5 alkyl, linear or branched C1-C5 halogenated alkyl, linear or branched O-(Ci-C 5 )-alkyl, linear or branched N-(Ci-C 5 )-alkyl, linear or branched (Ci-C 8 )-perfluoroalkyl, linear or branched O-(Ci-C 8 )-perfluoroalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl; preferably selected from linear or branched C1-C5 alkyl, linear or branched O-(C C 5 )-alkyl, linear or branched O-(Ci-C 8 )-perfluoroalkyl, and substituted or unsubstit
  • p, q, r and s are independently selected from 1 and 2; u and v are independently selected from 0, 1 , 2, 3 and 4; and
  • R 1 , R 2 , R 3 and R 4 are t-Bu; p, q, r and s are 2; R 1 , R 2 , R 3 and R 4 are in positions 3, 5, 3’ and 5’ of the biphenyl rings; 0 ⁇ m ⁇
  • u and v are 0.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from linear or branched C1-C5 alkyl, linear or branched C1-C5 halogenated alkyl, linear or branched O-(Ci-C 5 )-alkyl, linear or branched N-(Ci-C 5 )-alkyl, linear or branched (Ci-C 8 )-perfluoroalkyl, linear or branched O-(Ci-C 8 )-perfluoroalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl; preferably selected from linear or branched C1-C5 alkyl, linear or branched O-(C C 5 )-alkyl, linear or branched O-(Ci-C 8 )-perfluoroalkyl, and substituted or unsubstit
  • p, q, r and s are independently selected from 1 and 2; and u and v are independently selected from 1 , 2, 3 and 4; in the presence of an organic base, preferably selected from pyridine, diisopropylethylamine, 1 -methylimidazole, butyllithium, and triethylamine(alone or in combination with catalytic amounts of 4-dimethylaminopyridine).
  • organic base is triethylamine.
  • Tetraethylene glycol was slowly added via cannula to the chlorophosphite solution (ca. 30 min) at room temperature. Then, the mixture was stirred for 16 hours. After this, the turbid reaction mixture was filtered through celite® and the filtrate was evaporated to dryness to give the crude as a white-yellow solid. The product was then purified by filtration through a pad of basic alumina, using dichloromethane as the solvent, to give the pure bisphosphite(LI) as white solid (1.86 g, 92% isolated yield, melting point 92 °C, HRMS (ESI + ) m/z calcd. for C64H 97 O9P2 + [M+H] + 1071.6602, found 1071.6597). Spectroscopic data of the compoundwere in agreement with the proposed structure.
  • step 1 The synthetic route to the target compound 4 (step 1) was previously reported in Vidal-Ferran et a!., Chem. Eur. J., 2015, 21 , 11417-11426.
  • the monotosylated product 4 was prepared from a solution of triethylene glycol 3 (7.83 mL, 55.5 mmol, 1 equiv.) and triethylamine (4.0 mL, 28.5 mmol, 0.514 equiv.) in CH 2 CI 2 (100 mL). Then, tosyl chloride (2.71 g, 13.9 mmol, 0.251 equiv.) was added in one portion. The resulting mixture was stirred for two hours at room temperature. After washing with 100 mL of 1 M KHSO 4 and 5% NaHCO 3 and drying over Na 2 SO 4 , the product was obtained by purification by flash column chromatography over silica gel using AcOEt as eluent.
  • step 2 The synthetic route to the target compound 6 (step 2) was previously reported in Vidal-Ferran et a/., Chem. Eur. J., 2015, 21 , 11417-11426.
  • the diol 6 was slowly added via cannula to the chlorophosphite solution (ca. 30 min) at room temperature. Then, the mixture was stirred for 18 hours. After this, the turbid reaction mixture was filtered through celite® and the filtrate was evaporated to dryness to give the crude as a white-yellow solid. The product was then purified by filtration through a pad of basic alumina, using dichloromethane as the solvent, to give the pure bisphosphite L2 as white solid (2.98 g, 89% isolated yield, melting point 81 °C, HRMS (ESI + ) m/z calcd. for C 8 oH 112 NaOi 2 P2 + [M+Na] + 1349.7521 , found 1349.7527). Spectroscopic data of the compound were in agreement with the proposed structure.
  • Triethylamine (418 pL, 2.98 mmol, 2.4 equiv.) was then added dropwise.
  • a solution of heptaethylene glycol (359 pL, 1.24 mmol, 1.0 equiv.), previously azeotropically dried with toluene (3 x 5 mL), in 5 mL anhydrous toluene (SPS) was prepared.
  • Heptaethylene glycol was slowly added via cannula to the chlorophosphite solution (ca. 30 min) at room temperature. Then, the mixture was stirred for 16 hours.
  • the solvents can also be removed in vacuo to dryness.
  • the resulting solid is stable if stored at low temperature (below 0 °C) under a CO atmosphere.
  • the solvents can also be removed in vacuo to dryness.
  • the resulting solid is stable if stored at low temperature (below 0 °C) under a CO atmosphere.
  • the solvents can also be removed in vacuo to dryness.
  • the resulting solid is stable if stored at low temperature (below 0 °C) under a CO atmosphere.
  • the solvents can also be removed in vacuo to dryness.
  • the resulting solid is stable if stored at low temperature (below 0 °C) under a CO atmosphere.
  • Rh-mediated asymmetric hydroformylation was performed according to the following general procedure.
  • the autoclave was purged three times with H 2 /CO (1 :1) (pressure not higher than 10 bar) and finally, the autoclave was pressurized with H 2 /CO (1 :1) to the desired pressure (10 bar).
  • the reaction mixture was stirred at 60°C for 18 hours.
  • the reaction was cooled and the pressure was carefully released in a well- ventilated hood. Conversion, chemo- and regio-selectivity of the products arising from hydroformylation reaction conditions were determined by GC analysis on an achiral stationary phase (HP-5) using dodecane as the internal standard.
  • Table I a Thesehydroformylations were performed with 1 mol% of the supramolecular catalysts prepared in advance (according to the recipe disclosed in Example 7). The results in terms of conversion and selectivity were in agreement with those obtained with the catalyst prepared in situ (results indicated in this table in entries 4 and 6) ⁇ 1%.
  • Table VII aThese hydroformylations were performed with 1 mol% of the supramolecular catalysts prepared in advance (according to the recipe disclosed in Example 7). The results in terms of conversion and selectivity were in agreement with those obtained with the catalyst prepared in situ (results indicated in this table in entries 4 and 6) ⁇ 2%.
  • Example 18 Rh-mediated asymmetric hydroformylation of 1-((2-methylallyl)oxy)octane Aldehyde products

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Abstract

L'invention concerne un catalyseur d'hydroformylation de formule (I), qui comprend un complexe de rhodium. L'invention concerne également un procédé de préparation du catalyseur, et l'utilisation du catalyseur dans des réactions d'hydroformylation qui présentent une régiosélectivité supérieure en faveur d'aldéhydes linéaires, ainsi que des rendements de conversion plus élevés. L'invention concerne également un ligand et un procédé de préparation du ligand. Elle concerne en outre un procédé de préparation d'aldéhydes par une réaction d'hydroformylation.
EP24715729.0A 2023-03-30 2024-03-22 Catalyseur d'hydroformylation supramoléculaire Pending EP4688797A2 (fr)

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