WO2020073180A1 - Utilisation du 2,6-diisopropylaniline de lithium dans la catalyse d'hydroboration d'imine avec du borane - Google Patents

Utilisation du 2,6-diisopropylaniline de lithium dans la catalyse d'hydroboration d'imine avec du borane Download PDF

Info

Publication number
WO2020073180A1
WO2020073180A1 PCT/CN2018/109375 CN2018109375W WO2020073180A1 WO 2020073180 A1 WO2020073180 A1 WO 2020073180A1 CN 2018109375 W CN2018109375 W CN 2018109375W WO 2020073180 A1 WO2020073180 A1 WO 2020073180A1
Authority
WO
WIPO (PCT)
Prior art keywords
imine
borane
add
lithium
reaction
Prior art date
Application number
PCT/CN2018/109375
Other languages
English (en)
Chinese (zh)
Inventor
薛明强
颜丹丹
陈素芳
朱章野
蔡玲霞
沈琪
Original Assignee
南通纺织丝绸产业技术研究院
苏州大学
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.)
Filing date
Publication date
Application filed by 南通纺织丝绸产业技术研究院, 苏州大学 filed Critical 南通纺织丝绸产业技术研究院
Priority to PCT/CN2018/109375 priority Critical patent/WO2020073180A1/fr
Publication of WO2020073180A1 publication Critical patent/WO2020073180A1/fr

Links

Classifications

    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/04—Esters of boric acids

Definitions

  • the invention relates to the application of 2,6-diisopropylaniline lithium, in particular to the high-efficiency application of 2,6-diisopropylaniline lithium in the catalytic hydroboration reaction of imine and borane.
  • the borohydride reaction of imines has become a research hotspot in recent years.
  • the reported catalysts used in the borohydride reaction of imines mainly include the catalytic systems of main group elements: magnesium, calcium, sodium, rhenium, zinc, etc. (see Manna, K .; Ji, P .; Greene, FX; Lin, WJAm. Chem. Soc. 2016, 138, 7488-7491; Lin, YC .; Hatzakis, E .; McCarthy, SM; Reichl, KD; Lai, TY. ; Yennawar, HP; Radosevich, ATJAm. Chem. Soc. 2017, 139, 6008-6016).
  • the purpose of the invention of the present invention is to provide the application of 2,6-diisopropylaniline lithium, that is, the application of 2,6-diisopropylaniline lithium as a high-efficiency catalyst to catalyze the hydroboration reaction of imine and borane.
  • the technical scheme adopted by the present invention is: the application of lithium 2,6-diisopropylaniline in catalytic borohydride reaction of aldehyde and borane; the 2,6-diisopropylaniline
  • the chemical formula of lithium is: 2,6- i Pr 2 PhNHLi.
  • the invention also discloses a method for 2,6-diisopropylanilinyl lithium to catalyze the borohydride reaction between imine and borane, which includes the following steps: dehydrated and deoxygenated under anhydrous and oxygen-free environment and inert gas atmosphere Add imine to the reaction bottle, add organic solvent, then add borane, mix well, then add the catalyst 2,6-diisopropylanilinyl lithium, react for 1h ⁇ 2h, and terminate the reaction by exposure to air to obtain the product.
  • the invention further discloses a method for preparing a borate ester, which includes the following steps: adding an imine to a reaction flask subjected to dehydration and deoxygenation under an inert gas atmosphere under an anhydrous and oxygen-free environment, adding an organic solvent, and then adding Borane, mixed evenly, then added catalyst 2,6-diisopropylanilinium lithium, reacted for 1h ⁇ 2h, and exposed to air to terminate the reaction to obtain the product.
  • the imine is selected from aldimine; the general chemical structure of the imine is as follows:
  • R 1 or R 2 is one of an electron-withdrawing group or an electron-donating group, which may be selected from halogen, methyl, and methoxy; the borane is selected from pinacol borane.
  • the amount of the catalyst may be 4% to 5% of the number of moles of imine, and the molar ratio of imine to pinacol borane is 1: 1 to 1: 1.2.
  • the reaction temperature is room temperature
  • the reaction time is 1 to 2 hours.
  • the organic solvent is tetrahydrofuran.
  • the present invention has the following advantages compared with the prior art:
  • the present invention finds for the first time that simple 2,6-diisopropylanilinyl lithium can efficiently catalyze the borohydride reaction between imine and borane, which is highly consistent with the economical synthesis of atoms.
  • the 2,6-diisopropylanilinium lithium catalyst disclosed in the present invention has a high catalytic activity for the hydroboration reaction of imine and borane (4 to 5% of the moles of catalyst used), and the reaction conditions are mild (room temperature) , The reaction time is short (1h ⁇ 2h), and the reaction yield is high, the reaction is simple and controllable, the post-treatment is simple, and the reaction uses inexpensive THF as the solvent.
  • the catalyst disclosed in the present invention has good universality for imines with different substitution positions and different electronic effects.
  • Embodiment 2 2,6-diisopropylanilinyl lithium catalyzes the hydroboration reaction of benzylidene and pinacol borane
  • Embodiment 5 2,6-diisopropylanilinyl lithium catalyzes the hydroboration reaction of benzylidene and pinacol borane
  • Example 8 2,6-diisopropylanilinyl lithium catalyzes the hydroboration of N- (4-fluorobenzylidene) aniline with pinacol borane
  • Example 11 2,6-diisopropylanilinyl lithium catalyzes the hydroboration of benzylidene-p-toluidine with pinacol borane
  • the reaction temperature of the above embodiment is room temperature; the present invention discloses for the first time that commercial reagent 2,6-diisopropylanilinyl lithium can catalyze the borohydride reaction of imine under mild reaction conditions, with high yield and wide range The applicable scope of the substrate, cheap catalyst and mild catalytic conditions provide the possibility for industrial application.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)

Abstract

La présente invention concerne une utilisation du 2,6-diisopropylaniline de lithium, et concerne plus particulièrement une utilisation du 2,6-diisopropylaniline de lithium dans la catalyse d'hydroboration d'imine avec du borane. La présente invention consiste à agiter de manière séquentielle et combiner complètement un catalyseur, un borane et une imine, faire réagir pendant 1 à 2 heures, et exposer à l'air pour terminer la réaction. Le solvant dans la solution de réaction est éliminé sous pression réduite pour obtenir des borates ayant différents substituants. La 2,6-diisopropylaniline de lithium fournie par l'invention peut catalyser l'hydroboration de l'imine par du borane avec une activité élevée à température ambiante. La quantité de catalyseur utilisée est de 4 à 5 % en moles des moles d'imine, et le rendement de la réaction peut être de 90 % ou plus. Par comparaison avec des systèmes catalytiques existants, la présente invention utilise simplement du 2,6-diisopropylaniline de lithium, a des conditions de réaction modérées, et le rendement des borates ayant différents substituants peut atteindre 99 % dans des conditions optimisées.
PCT/CN2018/109375 2018-10-08 2018-10-08 Utilisation du 2,6-diisopropylaniline de lithium dans la catalyse d'hydroboration d'imine avec du borane WO2020073180A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2018/109375 WO2020073180A1 (fr) 2018-10-08 2018-10-08 Utilisation du 2,6-diisopropylaniline de lithium dans la catalyse d'hydroboration d'imine avec du borane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2018/109375 WO2020073180A1 (fr) 2018-10-08 2018-10-08 Utilisation du 2,6-diisopropylaniline de lithium dans la catalyse d'hydroboration d'imine avec du borane

Publications (1)

Publication Number Publication Date
WO2020073180A1 true WO2020073180A1 (fr) 2020-04-16

Family

ID=70163756

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/109375 WO2020073180A1 (fr) 2018-10-08 2018-10-08 Utilisation du 2,6-diisopropylaniline de lithium dans la catalyse d'hydroboration d'imine avec du borane

Country Status (1)

Country Link
WO (1) WO2020073180A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108503660A (zh) * 2018-04-16 2018-09-07 苏州大学 苯胺基锂在催化醛和硼烷硼氢化反应中的应用
CN108503659A (zh) * 2018-04-16 2018-09-07 苏州大学 利用2,6-二异丙基苯胺基锂制备硼酸酯的方法
CN108558924A (zh) * 2018-04-16 2018-09-21 南通纺织丝绸产业技术研究院 邻甲基苯胺基锂在催化酮和硼烷硼氢化反应中的应用
CN108558925A (zh) * 2018-04-16 2018-09-21 南通纺织丝绸产业技术研究院 2,6-二异丙基苯胺基锂在催化酮和硼烷硼氢化反应中的应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108503660A (zh) * 2018-04-16 2018-09-07 苏州大学 苯胺基锂在催化醛和硼烷硼氢化反应中的应用
CN108503659A (zh) * 2018-04-16 2018-09-07 苏州大学 利用2,6-二异丙基苯胺基锂制备硼酸酯的方法
CN108558924A (zh) * 2018-04-16 2018-09-21 南通纺织丝绸产业技术研究院 邻甲基苯胺基锂在催化酮和硼烷硼氢化反应中的应用
CN108558925A (zh) * 2018-04-16 2018-09-21 南通纺织丝绸产业技术研究院 2,6-二异丙基苯胺基锂在催化酮和硼烷硼氢化反应中的应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LAWSON, JAMES R. ET AL.: "Tris (2, 4, 6-trifluorophenyl) Borane: An Efficient Hydroboration Catalyst", CHEM.EUR.J., vol. 23, no. 46, 27 July 2017 (2017-07-27), pages 11000, XP055701118, ISSN: 1521-3765 *
YAN, DANDAN ET AL.: "Highly Efficient Hydroboration of Carbonyl Compounds Catalyzed by Tris (Methylcyclopentadienyl) lanthanide Complexes", ORG.BIOMOL.CHEM., vol. 16, no. 15, 26 March 2018 (2018-03-26), pages 2789, XP055701115, ISSN: 1477-0539 *

Similar Documents

Publication Publication Date Title
CN109331872B (zh) 正丁基锂在催化亚胺和硼烷硼氢化反应中的应用
CN107930696B (zh) 三甲茂稀土配合物在催化亚胺和硼烷的硼氢化反应中的应用
CN112321628B (zh) β-二甲基苯基硅取代有机腈类化合物的制备方法
US11680075B2 (en) Application of 4-MePhNHLi in catalyzing hydroboration reaction of imine and borane
CN105753715A (zh) 一种胺的甲基化方法
CN101664699B (zh) 一种用于制备酰胺化合物的催化剂及其应用
CN109331867B (zh) 2,6-二甲基苯胺基锂在催化亚胺和硼烷硼氢化反应中的应用
CN109289914B (zh) 邻甲基苯胺基锂在催化亚胺和硼烷硼氢化反应中的应用
CN109251217B (zh) 邻甲氧基苯胺基锂在催化亚胺和硼烷硼氢化反应中的应用
WO2020073180A1 (fr) Utilisation du 2,6-diisopropylaniline de lithium dans la catalyse d'hydroboration d'imine avec du borane
US11891408B2 (en) Application of lithium 4-methoxyaniline in catalysis of hydroboration reaction of imine and borane
CN107501338B (zh) 一种2,6-二氨基吡啶缩4-羧基苯甲醛双希夫碱钴配合物的制备方法
US11845068B2 (en) Use of n-butyllithium for catalyzing hydroboration of imine and borane
CN107235845B (zh) 一种非金属催化的三级芳香酰胺双向选择性还原的新方法
WO2020073178A1 (fr) Utilisation du-o-méthylaniline-lithium dans la catalyse d'hydroboration d'une imine avec le borane
WO2020073177A1 (fr) Utilisation du 2,6-diméthylaniline-lithium dans la catalyse d'hydroboration d'une imine avec le borane
WO2020073176A1 (fr) Utilisations d'anilide de lithium dans la catalyse d'une réaction d'hydroboration d'imine et de borane
JP2002053542A (ja) 環状脂肪族の第１級ビシナルジアミンのシアノエチル化
CN109232622B (zh) 2,6-二异丙基苯胺基锂在催化亚胺和硼烷硼氢化反应中的应用
CN109180714B (zh) 苯胺基锂在催化亚胺和硼烷硼氢化反应中的应用
CN109289913B (zh) 4-甲氧基苯胺基锂在催化亚胺和硼烷硼氢化反应中的应用
WO2020073181A1 (fr) Utilisation de o-méthoxyaniline lithium dans la catalyse d'une réaction d'hydrogénation de bore d'imine et de borane
CN109251216B (zh) 对甲基苯胺基锂在催化亚胺和硼烷硼氢化反应中的应用
CN107513078B (zh) 一种2,6-二氨基吡啶缩3-羧基苯甲醛双希夫碱钴配合物的制备方法
CN107513079B (zh) 一种2,6-二氨基吡啶缩邻羧基苯甲醛双希夫碱钴配合物的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18936756

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18936756

Country of ref document: EP

Kind code of ref document: A1