WO2018106336A1 - Catalyseurs de palladium mono-ligaturés, leur synthèse et leur utilisation dans un couplage de suzuki - Google Patents

Catalyseurs de palladium mono-ligaturés, leur synthèse et leur utilisation dans un couplage de suzuki Download PDF

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WO2018106336A1
WO2018106336A1 PCT/US2017/055736 US2017055736W WO2018106336A1 WO 2018106336 A1 WO2018106336 A1 WO 2018106336A1 US 2017055736 W US2017055736 W US 2017055736W WO 2018106336 A1 WO2018106336 A1 WO 2018106336A1
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aryl
alkyl
formula
composition according
group
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PCT/US2017/055736
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English (en)
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Chunming Zhang
Kelli A. OGAWA
Siyu TU
James W. Ringer
Christopher W. Derstine
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Dow Global Technologies Llc
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/04—Substitution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides

Definitions

  • This invention relates generally to palladium catalysts and their method of manufacture.
  • Transition metal e.g. palladium, nickel, or platinum
  • aryl halide iodide, bromide, chloride
  • aryl pseudohalides e. g. triflate, tosylate, mesylate, fluorosulfonate
  • the activity of transition metal catalysts is greatly influenced by the structural features and the number of associated ligands to the metal. Mono-ligated Pd(0) catalysts, bearing one bulky and electron-rich ligand, have been demonstrated to be effective.
  • Mono-ligated Pd(0) catalysts have been generated in situ from mono-ligated palladium (II) precatalysts, such as the biphenyl palladacycle precatalyst described in prior art WO2013/184198 Al by Buchwald, and the mono-ligated allylpalladium (II) complex described in prior art WO2011161451 Al by Colacot. See also Chen et. al, Tri(l-adamantyl)phosphine: Expanding the Boundary of Electron-Releasing Character Available to Organophosphorous Compounds, J. Am. Chem. Soc. 2016, 138, 6392-6395.
  • the present inventors have discovered mono-ligated palladium catalysts that are easy to synthesize and are effective in Suzuki coupling reactions.
  • the invention is a composition comprising a
  • Y is OR 6 where R 6 is alkyl or aryl, or Y is NR 7 Rs wherein R 7 , Rs are each independently, H, alkyl, aryl; and
  • Ri - R 4 are each independently, H, alkyl, aryl, alkoxy, aryloxy; Ri and R2, R2 and R3, or R3 and R 4 form a cycle; and
  • R5 is H, alkyl, or aryl.
  • a method for making the compound of formula I comprising reacting formula III in a solvent with a Pd(II) source and an acid (HX) at a temperature in the range of 0 °C to 100 °C and then reacting Formula II with two ligands, L, at 0 °C to 40 °C in a polar aprotic
  • a method comprising reacting an aryl halide or pseudohalide with an organoboron compound in the presence of compound of Formula I.
  • Ri - R 4 are selected from hydrogen, alkyl, and alkyloxy, where the alkyl and alkyloxy, preferably have from 1 to 20, more preferably 1 to 10, and most preferably 1-6 carbon atoms.
  • R5 is preferably selected from hydrogen and alkyl (of preferably 1 to 20, more preferably 1 to 10, and most preferably 1-6 carbon atoms).
  • R 7 and Rs are hydrogen and alkyl groups (preferably of 1 to 20, more preferably 1 to 10, and most preferably 1-6 carbon atoms).
  • R 7 and Rs may by alkyl groups which combine to form a cyclic group.
  • the precatalyst has Formulae 1-5 or 1-6 (Embodiments of Formula I and Formula 1-1 and where Ri, R2, R 4 , and R5 are H, R3 is as shown, and Y is OR 6 and R 6 is as defined above, and X and L are as defined herein)
  • the precatalyst has Formulae 1-7 or 1-8 (embodiments of
  • Y is NR7R8 and R7 and Rs are as defined above, and X and L are as defined herein)
  • the precatalyst has Formulae 1-9 or I- 10 (subspecies of
  • the precatalyst has Formulae 1-11 or 1-12 (subspecies of Formula 1-7 and 1-8 where R 7 and Rs are methyl ("Me"))
  • precatalysts include those selected from the group of
  • the precatalyst of this invention can contain any of a variety of known ligands.
  • the preferred ligands are trialkylphosphine, triarylphosphine, dialkylarylphosphine, alkyldiarylphosphine, bis(phosphine), phosphoramide, or N-heterocyclic carbene.
  • the ligands may be selected from the group consisting of triphenylphosphine (PI13P), tri-t- butylphosphine(P(t-Bu)3), tricyclohexylphosphine (P(Cy)3) , tri(o-tolyl)phosphine( P(o- tol) 3 ), (+)-2,2'-Bis(diphenylphosphino)- 1 , 1 '-binaphthalene((+)-BINAP), 1,1'-
  • Me is methyl
  • i-Pr isopropyl
  • Cy is cyclohexyl
  • tBu is t-butyl
  • Ad is adamantyl
  • Xi is N or CH
  • R is alkyl, cycloalkyl or aryl of 1-20, preferably 1-10, more preferably 1-6 carbon atoms.
  • R x is alkyl (such as butyl, adamantyl (Ad), benzyl, aryl
  • N-heterocyclic carbene selected from imidazoline-2- lidenes of the formula
  • the anion X may be any anion but is preferably selected from group consisting of halide, alkylcarboxylate, boron tetrafluoride, tetraarylborates (such as B(C6H 5 )4 " , and (B[3,5-(CF3)2C6H3] 4 ) " ), alkylsulfonate, haloalkylsulfonate, and arylsulfonate.
  • the anion is a halide selected from fluoride, chloride, bromide or iodide.
  • X is alkylcarboxylate, and the alkyl is substituted or unsubstituted alkyl of 1 to 12 carbon atoms. Suitable substituents include halides (fluoro, chloro) and alkoxyl, aryloxyl, cyano, nitro, carbonyl. X may be acetate. X may be a haloalkylcarboxylate such as triflouroacetate (TFA) or trichloroacetate.
  • TFA triflouroacetate
  • X is alkylsulfonate, cycloalkyl or arylsulfonate, and the alkyl is a substituted or unsubstituted alkyl of 1 to 4 carbon atoms and the aryl may be a substituted or unsubstitued aryl of preferably 6 to 12 carbon atoms.
  • X may be methylsulfonate, ethylsulfonate, methylphenylsulfonate or p-toluenesulfonate (TsO ).
  • Suitable substituents include halides and alkoxyl, aryloxyl,cyano, nitro, carbonyl.
  • X may be fluoroalkylsulfonate, such as trifluoromethylsulfonate (TfO ), nonafluorobutane sulfonate (NfO-).
  • the invention relates to a method of making any one of the aforementioned precatalysts, according to Scheme 1 from a palladacycle dimer of Formula II
  • THF tetrahydrofuran
  • CH2CI2 methylene chloride
  • Conditions for the reaction may be in the range of 0 °C to about 40 °C.
  • the reaction should be allowed to run until substantially complete which may occur in the range of 30 minutes to 20 hours. It is preferable to perform the reactions under an inert atmosphere using a gas such as nitrogen or argon.
  • the dimers of Formula II may be obtained from any known source or may be made according to Scheme 2
  • the substrate of Formula III is obtained from a commercial source or prepared by known methods; X, Ri - R 5 , and Y are defined above.
  • the Pd(II) source may be any known suitable source but is preferably palladium acetate (Pd(OAc)2).
  • the solvent may be a non- polar or a polar aprotic solvent. Preferred solvents are toluene, methylene chloride, THF, or 1,4-dioxane.
  • the reaction in scheme 2 takes place at 20 °C to about 100 °C. The reaction is typically complete after about 30 minutes to 20 hours.
  • This invention also relates to the application of any one of the aforementioned precatalysts in Suzuki-Miyaura cross-coupling reactions of Scheme 3:
  • the precatalyst is any one of the aforementioned precatalysts
  • R9 is aryl, heteroaryl, alkyl, or alkenyl
  • Xi is I, Br, CI, or sulfonate (such as triflate, nonflate, tosylate, mesylate, fluorosulfonate);
  • Rio is aryl, alkenyl, or alkyl, preferably of from 1 to 20, more preferably 1 to 10, and most preferably 1-6 carbon atoms ;
  • boron functional group which is preferably selected from a group consisting of boronic acid, boronic ester (e.g. boronic acid binacol ester (BPin)), potasium trifluoroborate (-BF3K), N-methyliminodiacetic acid boronate (BMIDA), etc.
  • boronic ester e.g. boronic acid binacol ester (BPin)
  • BPin boronic acid binacol ester
  • -BF3K potasium trifluoroborate
  • BMIDA N-methyliminodiacetic acid boronate
  • An embodiment of this invention provides a process which comprises mixing, in a liquid medium, i) at least one base; ii) at least one aryl halide or aryl pseudohalide (as defined below) in which all substituents are other than boron functionalized groups, wherein the aryl halide has, directly bonded to the aromatic ring(s), at least one halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom, wherein aryl pseudohalide has, directly bonded to the aromatic ring(s), at least one pseudohalide group selected from sulfonates consisting of triflate (OTf), tosylate (OTs), nonflate, mesylate (OMs), and fluorosulfonate (SO2F); iii) at least one organoboron compound selected from arylboronic acid, arylboronic ester, aryltrifluoroborate, aryl-9
  • the liquid medium for the processes in this invention can include any of a wide range of solvents, and mixtures of solvents are also usable.
  • the types of solvents that can be used include hydrocarbons, ethers, amides, ketones, alcohols, nitriles (acetonitrile), dimethyl sulfoxide, and water. Polar solvents are preferred.
  • Ethers that may be used include, for example, 1 ,4-dioxane, tetrahydrofuran, glyme, diglyme.
  • a large variety of bases are suitable for the processes in this invention. Generally, these are inorganic bases. Alkali metal salts are a preferred group of inorganic bases.
  • alkali metal salts include, but are not limited to, sodium acetate, sodium bicarbonate, sodium carbonate, sodium tert-butoxide, sodium hydroxide, potassium bicarbonate, potassium carbonate, potassium phosphate, potassium hydroxide, potassium tert-botoxide, cesium bicarbonate, and cesium carbonate.
  • Alkali metal salts of carboxylic acid anions e.g., acetate
  • Amines e.g. triethylamine, pyridine
  • Choice(s) of base will vary with the particular system of aryl halide or pseudohalide and organoboron compound involved.
  • the aryl halide or pseudohalide has at least one halogen atom directly bonded to the aromatic ring(s) selected from a chlorine atom, a bromine atom, and a iodine atom, or at least one pseudohalide group.
  • the term "pseudohalide group” includes such groups as arylsulfonate (e.g., p-toluenesulfonate (tosylate)), alkylsulfonate (e.g., methanesulfonate, OMs; trifluoromethanesulfonate (triflate)), and fluorosulfonate.
  • the aryl moiety for the aryl halide or pseudohalide can be homocyclic or heterocyclic.
  • suitable homocyclic aryl moieties include, but are not limited to benzene, naphthalene, anthracene,
  • Heterocyclic aryl moieties that can be used include, for example, furan, thiophene, oxathiolane, nitrogen-containing heterocycles, such as pyridine, indole, and isoxazole, and the like.
  • the organoboron compond in this invention is selected from aryl organoboron compounds, alkenyl organoboron compounds, and alkyl organoboron compounds.
  • Suitable aryl organoboron compounds include arylboronic acid, arylboronic ester, aryl-BMIDA, aryltrifluoroborate, the aryl moieties are homocyclic or heteroyclic.
  • Corresponding alkenyl and alkyl boron compounds may also be used in this invention.
  • Suitable reaction temperature ranges are from 0 - 200 °C, preferably 20 - 80 °C.
  • An embodiment of this invention is the Suzuki coupling of aryl halide/pesudohalide and aryl boron compound to generate biaryl compounds, illustrated in Scheme 3a
  • the second embodiment of this invention is the Suzuki coupling of aryl
  • Ar is aryl groups (homocyclic or heterocyclic), Rn is an alkyl group, which can be non-cyclic or cyclic.
  • Rn is an alkyl group, which can be non-cyclic or cyclic.
  • the third embodiment of this invention is the Suzuki coupling of alkyl
  • R12 and R13 are each, independently, alkyl groups or cycloalkyl groups.
  • the other components and reaction conditions are as discussed above.
  • a flask e.g. 20 mL equipped with a magnetic stir bar and fitted with a rubber septum is charged with a substrate of Formula III (e.g. 5 mmol), Pd(OAc)2 ( e.g. 5 mmol), and a solvent (5 mL).
  • a substrate of Formula III e.g. 5 mmol
  • Pd(OAc)2 e.g. 5 mmol
  • a solvent mL
  • an acid HX such as e.g. trifluoroacetic acid (TFA), /?ara-toluenesulfonic acid monohydrate (TsOH)
  • MsOH methanesulfonic acid
  • TfOH trifluoromethanesulfonic acid
  • Example 2- Di ⁇ -tosyloxy-bis(2-ethoxycarbonylamino-m-tolyl-2C,0)dipalladium (II) (2) [0036] Following substantially General Procedure A, compound 2 below was made by reacting ethyl m-tolylcarbamate and p r -toluenesulfonic acid monohydrate in the presence of 1,4-dioxane and Pd(OAc)2 at ambient temperature for about 18 hours.
  • a flask e.g. 25 mL equipped with a magnetic stir bar, a nitrogen pad, and a rubber septum is charged with a palladacycle dimmer of Formula II (e.g. 0.5 mmol) and a solvent, such as THF (e.g. 5 mL) under nitrogen atmosphere.
  • a ligand 1.0 mmol in a solution or neat is then added.
  • the mixture is stirred at room temperature until the reaction is deemed complete (30 min to 20 h) by H-NMR or 31 P-NMR analysis.
  • hexane (10 mL) is added to the reaction mixture and stirred for 10 min.
  • the mixture is filtered, rinsed with hexane, and dried to afford the desired mono- ligated palladacycle precatalyst. If product does not precipitate, the solvent is evaporated under reduced pressure. The resulting residue is tritrated with hexane, filtered, rinsed with hexane, and dried to afford the desired mono-ligated palladacycle precatalyst.
  • a flask e.g. 25 mL tube flask equipped with a stir bar anda nitrogen pad was added an aryl halide (e.g. 1.0 mmol), an arylboronic acid (e.g. 1.1 mmol, 1.1 equiv.), octadecanol (internal standard, e.g. 0.50 mmol, 0. 50 equiv.), an organic solvent (e.g. 5 mL), water (e.g. 1 mL), and a base (e.g. 2.2 mmol, 2.20 equiv.).
  • aryl halide e.g. 1.0 mmol
  • an arylboronic acid e.g. 1.1 mmol, 1.1 equiv.
  • octadecanol internal standard, e.g. 0.50 mmol, 0. 50 equiv.
  • an organic solvent e.g. 5 mL
  • water e.g.
  • Table 1 shows data for Suzuki couplings conducted according to the scheme above using the stated precatalysts. Entries 6, 8, and 9 are comparative. Tables 2 and 3 show data for Suzuki couplings conducted according to the scheme above using precatalyst 3.
  • Yields were determined by H NMR spectroscopy an internal standard and are the average of 2 runs.
  • bData is from a single run.
  • bData is from a single run.
  • THF tetrahydrofuran
  • 1 ,4-dioxane 1,4-dioxane
  • toluene 1,4-dioxane/water and acetonitrile/water
  • alcohols methanol, ethanol, and isopropanol
  • THF/water and toluene/water solvent systems gave poor yields ( ⁇ 20%).
  • 1,4-dioxane/water and acetonitrile/water gave similar low yields.
  • a noticeable increase in yield was observed when alcohol solvents were used.
  • ethanol/water proved to be the best solvent system, giving an 89% yield after 1 h.
  • various inorganic bases were screened to find the optimal base.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne certains catalyseurs au palladium mono-ligaturés qui sont faciles à synthétiser et qui sont efficaces dans des réactions de couplage de Suzuki. Les catalyseurs mono-ligaturés comprennent une structure cyclique ayant un groupe substituant avec un atome d'azote adjacent à la structure cyclique et un atome d'oxygène associé à l'atome de palladium.
PCT/US2017/055736 2016-12-06 2017-10-09 Catalyseurs de palladium mono-ligaturés, leur synthèse et leur utilisation dans un couplage de suzuki WO2018106336A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011161451A1 (fr) 2010-06-23 2011-12-29 Johnson Matthey Plc Complexes
WO2013184198A1 (fr) 2012-06-08 2013-12-12 Massachusetts Institute Of Technology Palladacycles de type sulfonate de palladium à ligand phosphine

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011161451A1 (fr) 2010-06-23 2011-12-29 Johnson Matthey Plc Complexes
WO2013184198A1 (fr) 2012-06-08 2013-12-12 Massachusetts Institute Of Technology Palladacycles de type sulfonate de palladium à ligand phosphine

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEN: "Tri(l-adamantyl)phosphine: Expanding the Boundary of Electron-Releasing Character Available to Organophosphorous Compounds", J. AM. CHEM. SOC., vol. 138, 2016, pages 6392 - 6395, XP055380169, DOI: doi:10.1021/jacs.6b03215
DONG XUE ET AL: "Room-Temperature Stille Coupling of Tetraarylstannanes via Palladium-Catalyzed C-H Activation", SYNLETT, vol. 23, no. 13, 1 August 2012 (2012-08-01), DE, pages 1941 - 1946, XP055438660, ISSN: 0936-5214, DOI: 10.1055/s-0032-1316581 *
GANG CHENG ET AL: "Storable N-phenylcarbamate palladacycles for rapid functionalization of an alkyne-encoded protein", CHEMICAL COMMUNICATIONS, vol. 50, no. 79, 1 January 2014 (2014-01-01), pages 11679 - 11682, XP055438656, ISSN: 1359-7345, DOI: 10.1039/C4CC02969K *

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