WO2016183101A1 - Arylation catalysée par le palladium de fluoroalkylamines - Google Patents

Arylation catalysée par le palladium de fluoroalkylamines Download PDF

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Publication number
WO2016183101A1
WO2016183101A1 PCT/US2016/031675 US2016031675W WO2016183101A1 WO 2016183101 A1 WO2016183101 A1 WO 2016183101A1 US 2016031675 W US2016031675 W US 2016031675W WO 2016183101 A1 WO2016183101 A1 WO 2016183101A1
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WO
WIPO (PCT)
Prior art keywords
aryl
group
organic groups
catalyst
containing organic
Prior art date
Application number
PCT/US2016/031675
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English (en)
Inventor
Andrew T. BRUSOE
John F. Hartwig
Original Assignee
The Regents Of The University Of California
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by The Regents Of The University Of California filed Critical The Regents Of The University Of California
Publication of WO2016183101A1 publication Critical patent/WO2016183101A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
    • C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals

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

Abstract

L'invention concerne des procédés de synthèse de trifluoroéthylanilines, de difluoroéthylanilines, de pentafluoropropylanilines et de difluorophénéthylanilines par couplage catalysé par le palladium de fluoroalkylamines avec des bromures d'aryle et des chlorures d'aryle. Les réactions sont effectuées avec une base plus faible, telle que KOPh, en présence d'un catalyseur dérivé d'AdBippyPhos et de [Pd(allyle)Cl]2. Les réactions se produisent avec des charges de catalyseur inférieures à environ 0,50 % en moles et tolèrent la présence de divers groupes fonctionnels qui réagissent avec les bases fortes qui sont utilisées de manière caractéristique dans des réactions de couplage croisé C-N catalysées par Pd d'halogénures d'aryle. L'état résiduel du catalyseur est le complexe phénoxyde (BippyPhosPd(Ar)OPh) ; en raison de la propriété d'attraction d'électrons du substituant fluoroalkyle, l'étape limitant l'évolution de la réaction est l'élimination réductrice pour former la liaison C-N.
PCT/US2016/031675 2015-05-11 2016-05-10 Arylation catalysée par le palladium de fluoroalkylamines WO2016183101A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201562159816P 2015-05-11 2015-05-11
US62/159,816 2015-05-11

Publications (1)

Publication Number Publication Date
WO2016183101A1 true WO2016183101A1 (fr) 2016-11-17

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2016/031675 WO2016183101A1 (fr) 2015-05-11 2016-05-10 Arylation catalysée par le palladium de fluoroalkylamines

Country Status (1)

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WO (1) WO2016183101A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108997144A (zh) * 2018-07-13 2018-12-14 沅江华龙催化科技有限公司 一种铁卟啉催化芳香伯胺三氟乙基化的方法
CN108997145A (zh) * 2018-07-13 2018-12-14 沅江华龙催化科技有限公司 一种铁卟啉催化芳香仲胺三氟乙基化的方法
CN111116653A (zh) * 2020-01-02 2020-05-08 河北工业大学 一种吡唑联三氮唑膦化合物的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4871875A (en) * 1984-03-14 1989-10-03 Mitsui Toatsu Chemicals, Inc. Process for producing diphenylamines or N,N'-diphenylphenylenediamines
US20040044250A1 (en) * 2002-02-04 2004-03-04 Buchwald Stephen L. Transition-metal-catalyzed carbon-nitrogen bond-forming methods using carbene ligands
US20090234126A1 (en) * 2006-03-21 2009-09-17 Yale University Process for the Synthesis of Arylamines from the Reaction of an Aromatic Compound with Ammonia or a Metal Amide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4871875A (en) * 1984-03-14 1989-10-03 Mitsui Toatsu Chemicals, Inc. Process for producing diphenylamines or N,N'-diphenylphenylenediamines
US20040044250A1 (en) * 2002-02-04 2004-03-04 Buchwald Stephen L. Transition-metal-catalyzed carbon-nitrogen bond-forming methods using carbene ligands
US20090234126A1 (en) * 2006-03-21 2009-09-17 Yale University Process for the Synthesis of Arylamines from the Reaction of an Aromatic Compound with Ammonia or a Metal Amide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEN ET AL.: "Enantioselective Pd-Catalyzed Hydrogenation of Fluorinated Imines: Facile Access to Chiral Fluorinated Amines.", ORGANIC LETTERS, vol. 12, no. 21, 2010, pages 5075 - 5077, XP055329049, Retrieved from the Internet <URL:http://pubs.acs.org/doi/abs/10.1021/011020256> [retrieved on 20160711] *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108997144A (zh) * 2018-07-13 2018-12-14 沅江华龙催化科技有限公司 一种铁卟啉催化芳香伯胺三氟乙基化的方法
CN108997145A (zh) * 2018-07-13 2018-12-14 沅江华龙催化科技有限公司 一种铁卟啉催化芳香仲胺三氟乙基化的方法
CN108997145B (zh) * 2018-07-13 2021-01-15 沅江华龙催化科技有限公司 一种铁卟啉催化芳香仲胺三氟乙基化的方法
CN108997144B (zh) * 2018-07-13 2021-01-15 沅江华龙催化科技有限公司 一种铁卟啉催化芳香伯胺三氟乙基化的方法
CN111116653A (zh) * 2020-01-02 2020-05-08 河北工业大学 一种吡唑联三氮唑膦化合物的制备方法
CN111116653B (zh) * 2020-01-02 2022-08-12 河北工业大学 一种吡唑联三氮唑膦化合物的制备方法

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