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WO2018106337A1 - 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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Publication number
WO2018106337A1
WO2018106337A1 PCT/US2017/055737 US2017055737W WO2018106337A1 WO 2018106337 A1 WO2018106337 A1 WO 2018106337A1 US 2017055737 W US2017055737 W US 2017055737W WO 2018106337 A1 WO2018106337 A1 WO 2018106337A1
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Prior art keywords
aryl
alkyl
formula
independently
composition according
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English (en)
Inventor
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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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
    • 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
    • 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, fluorosulfnate
  • the activity of transition metal catalysts is greatly influenced by the structural features and the number of associated ligand to the metal. Mono-ligated Pd(0) catalysts, bearing one bulk and electron-rich ligand, havd been demonstrated to be effective.
  • Mono-ligated Pd(0) catalyst have been generated in situ from mono-ligated palladium (II) precatalysts, such as biphenyl palladacycle precatalyst described in prior art WO2013/184198 Al by Buchwald, and 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 Oroganophosphorous 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 compound of formula I
  • L is a ligand
  • Y is R 5 wherein R5 is H, alkyl, aryl, or Y is OR 6 where R 6 is alkyl or aryl, or Y is NR7R8 wherein R7, Rs are each independently, H, alkyl, aryl;
  • Z is O (oxygen), or NR9 wherein R9 is H, alkyl or aryl;
  • Ri -R4 are each independently, H, alkyl, aryl, alkoxy, aryloxy; Ri and R2, R2 and R3, or R3 and R 4 could form a cycle.
  • a method comprising 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 20 °C to 100 °C and then reacting Formula II with two ligands, L, at 0 °C to 100 °C in a
  • 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.
  • the precatalyst has Formulae I-l 1, 1-12 or 1-13 (subspecies of Formulae 1-8, 1-9 and 1-10 where R 7 and Rs are Me, and X and L are as defined herein):
  • 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-ylidenes of the formula or protonated salts thereof (which generate imidazoline-2-ylidenes in the presence of a base), wherein Ar is an aryl, R' and R", each are independently, hydrogen, halo, alkyl, or aryl. R' and R" are structures
  • the anion X may be any anion but is preferably selected from group consisting of halide, alkylcarboxylate, boron tetrafluoride, tetraarylborates (such as B(C6Hs)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
  • 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 accordi
  • the substrate of Formula III is obtained from a commercial source or prepared by known methods; X, Ri - R5, 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: precatalyst
  • the precatalyst is any one of the aforementioned precatalysts
  • Rio is aryl, heteroaryl, alkyl, or alkenyl
  • Xi is I, Br, CI, or sulfonate (such as triflate, nonflate, tosylate, mesylate,
  • Rii 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 is a 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 acid 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)
  • R12 is an alkyl group, which can be non-cyclic or cyclic.
  • the other components and reaction conditions are as discussed above.
  • the third embodiment of this invention is the Suzuki coupling of alkyl
  • R13 and Ri34 are each, independently, alkyl groups or cycloalkyl groups.
  • the other components and reaction conditions are as discussed above.

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

Abstract

La présente invention concerne certains catalyseurs au palladium mono-ligaturés qui sont faciles à synthétiser et qui sont efficaces dans des réactions de couplage de Suzuki. Ces catalyseurs sont caractérisés par un cycle aromatique ayant un groupe substituant comportant un atome d'oxygène adjacent au cycle aromatique et soit un atome d'oxygène soit un atome d'azote associé à l'atome de palladium.
PCT/US2017/055737 2016-12-06 2017-10-09 Catalyseurs de palladium mono-ligaturés, leur synthèse et leur utilisation dans un couplage de suzuki Ceased WO2018106337A1 (fr)

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US62/430,536 2016-12-06

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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 (4)

* Cited by examiner, † Cited by third party
Title
ALEX JOHN ET AL: "Palladium Catalyzed C-H Functionalization of O -Arylcarbamates: Selective ortho -Bromination Using NBS", THE JOURNAL OF ORGANIC CHEMISTRY, vol. 77, no. 13, 6 July 2012 (2012-07-06), US, pages 5600 - 5605, XP055428085, ISSN: 0022-3263, DOI: 10.1021/jo300713h *
AVILA-SORROSA ALCIVES ET AL: "Novel synthesis of a non-symmetric N1CN2Pd(II) pincer complex by a tandem reaction using ameta-hydroxylated imine ligand", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 819, 18 June 2016 (2016-06-18), pages 69 - 75, XP029703009, ISSN: 0022-328X, DOI: 10.1016/J.JORGANCHEM.2016.06.019 *
CHEN: "Tri(l-adamantyl)phosphine: Expanding the Boundary of Electron-Releasing Character Available to Oroganophosphorous Compounds", J. AM. CHEM. SOC., vol. 138, 2016, pages 6392 - 6395, XP055380169, DOI: doi:10.1021/jacs.6b03215
JOSÉ VICENTE ET AL: "Synthesis of Ortho-Palladated Phenol Derivatives. Study of Their Reactivity with Carbon Monoxide and Isonitriles", ORGANOMETALLICS, vol. 20, no. 13, 1 June 2001 (2001-06-01), US, pages 2704 - 2715, XP055428059, ISSN: 0276-7333, DOI: 10.1021/om010074z *

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