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Application of β-diimine divalent rare earth borohydride complexes in the catalytic hydroboration of ketones and boranes

A technology of β-diimine divalent rare earth and -diimine divalent rare earth, which is applied in the field of catalytic reaction of rare earth metal complexes to achieve high reaction efficiency, simple and controllable reaction process, and high yield

Active Publication Date: 2018-07-20
ZHANGJIAGANG INST OF IND TECH SOOCHOW UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In modern organic chemistry of rare earth metals, self-assembled rare earth metal complexes have become a class of highly active catalytic systems due to ligands with unique structures and highly efficient and controllable initiator groups. The report of complexes catalyzing the hydroboration reaction of borane and carbonyl compounds. In view of the high catalytic effect of this type of complexes, expanding the application of this type of complexes is not only of great application value, but also of great importance to the research of organoboron chemistry. theoretical significance

Method used

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  • Application of β-diimine divalent rare earth borohydride complexes in the catalytic hydroboration of ketones and boranes
  • Application of β-diimine divalent rare earth borohydride complexes in the catalytic hydroboration of ketones and boranes
  • Application of β-diimine divalent rare earth borohydride complexes in the catalytic hydroboration of ketones and boranes

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Embodiment one: [2,6- i pr 2 -(C 6 h 3 )-NC(Me)CHC(Me)N-(C 6 h 3 )-2,6- i pr 2 ]Yb-BH 4 . 2THF Catalyzed Hydroboration of Acetophenone and Pinacol Borane

[0025] Add 0.1 mL of catalyst [2,6- i pr 2 -(C 6 h 3 )-NC(Me)CHC(Me)N-(C 6 h 3 )-2,6- i pr 2 ]Yb-BH 4 . 2THF in toluene (0.01 M), then add pinacol borane (0.145 mL, 1 mmol) by syringe, and then add acetophenone (0.117 mL, 1 mmol) by syringe. After reacting for 5 min, add 0.5 mL CDCl 3 , to obtain NMR yield of 90% corresponding pinacol borate, C 6 h 5 CH(CH 3 )OB(OC(CH 3 ) 2 C(CH 3 ) 2 O). NMR data of the product: 1 H NMR (400 MHz, CDCl 3 ): 7.36 (d, 2H, Ar H ),7.16-7.11 (m, 3H, Ar H ), 5.25 (q, 1H, ArC H ), 1.49 (d, 3H, C H 3 CH), 1.21 (d,12H, C(C H 3 ) 2 ) ppm. 11 B NMR (128 MHz, CDCl 3 ): 25.8 ppm.

Embodiment 2

[0026] Embodiment two: [2,6- i pr 2 -(C 6 h 3 )-NC(Me)CHC(Me)N-(C 6 h 3 )-2,6- i pr 2 ]Sm-BH 4 . 2THF Catalyzed Hydroboration of Acetophenone and Pinacol Borane

[0027] Add 0.1 mL of catalyst [2,6- i pr 2 -(C 6 h 3 )-NC(Me)CHC(Me)N-(C 6 h 3 )-2,6- i pr 2 ]Sm-BH 4 . 2THF in toluene (0.01 M), then add pinacol borane (0.145 mL, 1 mmol) with a syringe, then add acetophenone (0.117 mL, 1 mmol) with a syringe, react for 10 min, then add 0.5 mL CDCl 3 , to obtain NMR yield of 92% corresponding pinacol borate, C 6 h 5 CH(CH 3)OB(OC(CH 3 ) 2 C(CH 3 ) 2 O). The NMR data of the product are the same as in Example 1.

Embodiment 3

[0028] Embodiment three: [2,6- i pr 2 -(C 6 h 3 )-NC(Me)CHC(Me)N-(C 6 h 3 )-2,6- i pr 2 ]Sm-BH 4 . 2THF-catalyzed hydroboration of o-methylacetophenone and pinacol-borane

[0029] Add 0.1 mL of catalyst [2,6- i pr 2 -(C 6 h 3 )-NC(Me)CHC(Me)N-(C 6 h 3 )-2,6- i pr 2 ]Sm-BH 4 . 2THF in toluene (0.01 M), then add pinacol borane (0.145 mL, 1 mmol) by syringe, and then add o-methylacetophenone (0.131 mL, 1 mmol) by syringe. After reacting for 10 min, add 0.5 mL CDCl 3 , to obtain NMR yield of 91% corresponding pinacol borate, C 6 h 5 CH(CH 3 )OB(OC(CH 3 ) 2 C(CH 3 ) 2 O). NMR data of the product: 1 H NMR (400 MHz, CDCl 3 ): 7.53 (d, 1H,Ar H ), 7.16 (td, 1H, Ar H ), 7.13 (td, 1H, Ar H ), 7.10 (t, 1H, Ar H ), 5.43 (q, 1H,ArC H ), 2.34 (s, 1H, ArC H 3 ), 1.45 (d, 3H, C H 3 CH), 1.21 (d, 12H, C(C H 3 ) 2 ) ppm. 11 B NMR (128 MHz, CDCl 3 ): 25.6 ppm.

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Abstract

The invention discloses application of a beta-diimide bivalent rare earth boron hydrogen complex in catalysis of hydroboration reaction of ketone and boron hydride. Beta-diimide rare earth dichloride and NaBH4 react in a tetrahydrofuran solvent, and in-situ Na / K reduction is carried out, so that the beta-diimide bivalent rare earth boron hydrogen complex, namely [2,6-ipr2-(C6H3)-NC(Me)CHC(Me)N-(C6H3)-2,6-ipr2]Ln-BH4.2THF, is obtained. The beta-diimide bivalent rare earth boron hydrogen complex disclosed by the invention can catalyze the hydroboration reaction of ketone and boron hydride with high activity under mild conditions and has the advantages of short reaction time and mild reaction conditions, and an aftertreatment method is simple and convenient.

Description

technical field [0001] The invention relates to a catalytic reaction of a rare earth metal complex, in particular to the application of a β-diimine divalent rare earth borohydride complex in catalyzing the hydroboration reaction of borane and ketone. Background technique [0002] The application of borates has been developed rapidly, such as trimethyl borate is widely used in the preparation of high-energy fuels; in addition, it is also used as anti-friction and anti-friction additives for lubricating oils, rubber-metal adhesion promoters, polymers Stabilizers, etc.; therefore, the synthesis of organic borates has always been a research hotspot. Reduction of boranes with carbonyl compounds such as ketones is the most direct and atom-economical method for the synthesis of boronic acid esters with different substituents. However, the reaction conditions are relatively harsh in the absence of catalysts. Therefore, the need to explore new catalytic systems for mild and efficie...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F5/04B01J31/22
CPCB01J31/2208B01J31/2217B01J2531/0213B01J2531/0241B01J2531/38C07F5/04
Inventor 薛明强洪玉标陈素芳沈琪
Owner ZHANGJIAGANG INST OF IND TECH SOOCHOW UNIV
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