WO2020073178A1 - Utilisation du-o-méthylaniline-lithium dans la catalyse d'hydroboration d'une imine avec le borane - Google Patents

Utilisation du-o-méthylaniline-lithium dans la catalyse d'hydroboration d'une imine avec le borane Download PDF

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Publication number
WO2020073178A1
WO2020073178A1 PCT/CN2018/109373 CN2018109373W WO2020073178A1 WO 2020073178 A1 WO2020073178 A1 WO 2020073178A1 CN 2018109373 W CN2018109373 W CN 2018109373W WO 2020073178 A1 WO2020073178 A1 WO 2020073178A1
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WO
WIPO (PCT)
Prior art keywords
imine
borane
add
lithium
reaction
Prior art date
Application number
PCT/CN2018/109373
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English (en)
Chinese (zh)
Inventor
薛明强
颜丹丹
武振杰
徐晓娟
朱章野
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.)
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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/CN2018/109373 priority Critical patent/WO2020073178A1/fr
Publication of WO2020073178A1 publication Critical patent/WO2020073178A1/fr

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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
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic 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 System
    • C07F5/02—Boron compounds
    • 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 System
    • C07F5/02—Boron compounds
    • C07F5/04—Esters of boric acids

Definitions

  • 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 lithium o-toluidine, that is, the application of lithium o-toluidine 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 o-toluidine in the catalytic hydroboration reaction of imine and borane; the chemical formula of lithium o-toluidine is: 2-MePhNHLi.
  • the invention also discloses a method for catalyzing the hydroboration reaction of imine and borane with lithium o-toluidine, which includes the following steps:
  • the invention further discloses a method for preparing boric acid ester, which includes the following steps:
  • 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 discloses for the first time that simple o-toluidine lithium can efficiently catalyze the borohydride reaction between imine and borane, which is highly consistent with the economical synthesis of atoms.
  • the lithium o-methylanilinyl 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), mild reaction conditions (room temperature), and short reaction time 1h ⁇ 2h), and the reaction yield is high, the reaction is simple and controllable, the post-treatment is simple, 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.
  • Example 1 Lithium o-toluidine catalyzes the hydroboration reaction of benzylidene and pinacol borane
  • Example 2 Lithium o-toluidine catalyzes the hydroboration reaction of benzylidene with pinacol borane
  • Example 3 Lithium o-toluidine catalyzes the hydroboration reaction of benzylidene aniline with pinacol borane
  • Example 4 Lithium o-methylanilinyl catalyzes the hydroboration reaction of benzylidene aniline with pinacol borane
  • Embodiment 5 Lithium o-methylanilinyl catalyzes the hydroboration reaction of N- (p-methylbenzylidene) aniline with pinacol borane
  • Example 6 Lithium o-toluidine catalyzes the hydroboration of N- (p-methoxybenzylidene) aniline with pinacol borane
  • Example 7 Lithium o-toluidine catalyzes the hydroboration of N- (4-fluorobenzylidene) aniline with pinacol borane
  • Example 8 Lithium o-toluidine catalyzes the hydroboration of N- (4-chlorobenzylidene) aniline with pinacol borane
  • Example 9 Lithium o-toluidine catalyzes the hydroboration of N- (4-bromobenzylidene) aniline with pinacol borane
  • Example 10 Lithium o-toluidine catalyzes the hydroboration of benzylidene-p-toluidine with pinacol borane
  • Example 11 Lithium o-toluidine catalyzes the hydroboration of N- (benzylidene) -4-fluoroaniline with pinacol borane
  • Example 12 Lithium o-toluidine catalyzes the hydroboration of N- (benzylidene) -4-chloroaniline with pinacol borane
  • Example 13 Lithium o-toluidine catalyzes the hydroboration of N- (benzylidene) -4-bromoaniline with pinacol borane
  • the reaction temperature of the above example is room temperature; the present invention discloses for the first time that the commercial reagent o-methylanilinyl lithium can catalyze the borohydride reaction of imine under mild reaction conditions, with a high yield and a wide range of substrate applications , Cheap catalysts and mild catalytic conditions provide the possibility for industrial applications.

Abstract

La présente invention concerne une utilisation du o-méthylaniline-lithium, et concerne spécifiquement une utilisation du o-méthylaniline-lithium dans la catalyse d'hydroboration d'une imine avec le borane. Un catalyseur, le borane et une imine sont séquentiellement agités et intimement combinés, réagissent pendant 1 à 2 heures, et sont exposés à l'air pour terminer la réaction. Le solvant dans la solution de réaction est éliminé sous pression réduite afin d'obtenir des borates comprenant différents substituants. Le o-méthylaniline-lithium de l'invention peut catalyser l'hydroboration d'une imine avec le 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 les systèmes catalytiques existants, la présente invention utilise simplement du o-méthylaniline-lithium, présente des conditions de réaction douces, et le rendement des borates comprenant différents substituants peut atteindre 99 % dans des conditions optimisées.
PCT/CN2018/109373 2018-10-08 2018-10-08 Utilisation du-o-méthylaniline-lithium dans la catalyse d'hydroboration d'une imine avec le borane WO2020073178A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2018/109373 WO2020073178A1 (fr) 2018-10-08 2018-10-08 Utilisation du-o-méthylaniline-lithium dans la catalyse d'hydroboration d'une imine avec le borane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2018/109373 WO2020073178A1 (fr) 2018-10-08 2018-10-08 Utilisation du-o-méthylaniline-lithium dans la catalyse d'hydroboration d'une imine avec le borane

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006028977A2 (fr) * 2004-09-02 2006-03-16 The Penn State Research Foundation Composes chiraux spiraniques et leur utilisation dans des reactions catalytiques asymetriques
US20180044354A1 (en) * 2016-08-09 2018-02-15 Chevron Phillips Chemical Company Lp Olefin Hydroboration
CN108164555A (zh) * 2016-06-30 2018-06-15 苏州大学 一种硼酸酯的合成方法
CN109289914A (zh) * 2018-09-27 2019-02-01 苏州大学张家港工业技术研究院 邻甲基苯胺基锂在催化亚胺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
WO2006028977A2 (fr) * 2004-09-02 2006-03-16 The Penn State Research Foundation Composes chiraux spiraniques et leur utilisation dans des reactions catalytiques asymetriques
CN108164555A (zh) * 2016-06-30 2018-06-15 苏州大学 一种硼酸酯的合成方法
US20180044354A1 (en) * 2016-08-09 2018-02-15 Chevron Phillips Chemical Company Lp Olefin Hydroboration
CN109289914A (zh) * 2018-09-27 2019-02-01 苏州大学张家港工业技术研究院 邻甲基苯胺基锂在催化亚胺和硼烷硼氢化反应中的应用

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