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Synthesis method of bidentate phosphorene ligand

A technology for a bidentate phosphene and a synthesis method is applied in the field of synthesis of a bidentate phosphene ligand, which can solve the problems of complex steps of the bidentate phosphene ligand, single product structure, complicated operation process, etc. The effect of efficient synthesis process and simple operation process

Active Publication Date: 2020-08-28
HUBEI UNIV
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  • Application Information

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Problems solved by technology

[0014] In view of this, the application provides a bidentate phosphine ligand and its simple, efficient, economical and serial synthesis method, using commercial raw materials and cheap catalysts to solve the problem of the bidentate phosphine ligand in the prior art. In order to solve the problems of complex steps, high cost of raw materials, small substrate range, single product structure, and complicated operation process, a series of bidentate phosphine ligands with steric effects and electronic properties have been developed.

Method used

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  • Synthesis method of bidentate phosphorene ligand
  • Synthesis method of bidentate phosphorene ligand
  • Synthesis method of bidentate phosphorene ligand

Examples

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Embodiment 1

[0035] Bidentate phosphine ligand 3a (2'-(4-methoxystyryl)-[1,1'-biphenyl]-2-yl)diphenylphosphine, the synthetic route is as follows:

[0036]

[0037] Add 101.4 mg (0.3 mmol) 2-diphenylphosphine-biphenyl 1a, 190.8 mg 1-(2-bromovinyl)-4-methoxybenzene 2a (E:Z=5.7:1) into the reaction kettle (0.9mmol), 3.8mg p-cymene dichloride ruthenium dimer, 7.8mg N-Ac-glycine, 49.2mg sodium acetate and 1mL methyl tert-butyl ether, stir and mix evenly and pass argon into the reaction system gas, control the reaction in an argon atmosphere, and react at 120°C for 16 hours, then cool to room temperature, filter with diatomaceous earth, and separate by column chromatography after vacuum distillation to obtain the E-form product 3aa(2'-(4-form Oxystyryl)-[1,1'-biphenyl]-2-yl)diphenylphosphine 83.2mg (59% yield), Z formula product 3ab(2'-(4-methoxybenzene Vinyl)-[1,1'-biphenyl]-2-yl)diphenylphosphine 40.9mg (29% yield), total product 3a mass 124.1mg, total yield 88% (E:Z=2.0 :1).

[0038] W...

Embodiment 2

[0045] Bidentate phosphine ligand 3b(E)-4-(2-(diphenylphosphino)phenyl)-3-(4-methoxystyryl)pyridine, the synthetic route is as follows:

[0046]

[0047] Add 101.7mg (0.3mmol) 4-(2-(diphenylphosphino)phenyl)pyridine 1b, 190.8mg1-(2-bromovinyl)-4-methoxybenzene 2a (E: Z=5.7:1)(0.9mmol), 3.8mg p-cymene dichloride ruthenium dimer, 7.8mg N-Ac-glycine, 49.2mg sodium acetate and 1mL methyl tert-butyl ether, after mixing evenly Pass argon into the reaction system, control the reaction in an argon atmosphere, and react at 160°C for 16 hours, then cool to room temperature, filter with diatomaceous earth, and distill under reduced pressure, and then separate by column chromatography to obtain 82.0 mg of the target product 3b. The yield was 58% (product of formula E only). 1 H NMR (400MHz, CDCl 3 )δ8.85(s, 1H), 8.31(d, J=5.2Hz, 1H), 7.42(td, J=7.2Hz, J=1.2Hz, 1H), 7.36(td, J=7.6Hz, J= 1.6Hz,1H),7.33-7.27(m,3H),7.20-7.11(m,11H),6.93-6.88(m,2H),6.83(d,J=8.4 Hz,2H),6.48(d,J =16.4Hz,1...

Embodiment 3

[0049] Bidentate phosphine ligand 3c (2'-(4-methoxystyryl)-4-methyl-[1,1'-biphenyl]-2-yl)diphenylphosphine, the synthetic route is as follows:

[0050]

[0051] Add 110.9 mg (0.3 mmol) (4-methyl-[1,1'-biphenyl]-2-yl) diphenylphosphine 1c, 190.8 mg 1-(2-bromovinyl)-4 -Methoxybenzene 2a (E:Z=5.7:1) (0.9mmol), 3.8mg p-cymene dichloride ruthenium dimer, 7.8mg N-Ac-glycine, 49.2mg sodium acetate and 1mL methyl For tert-butyl ether, stir and mix evenly, pass argon into the reaction system, control the reaction in an argon atmosphere, the temperature is at 120°C for 16 hours, then cool to room temperature, filter with diatomaceous earth, and distill under reduced pressure. Chromatography gave 127.8 mg of the target product 3c in a yield of 88% (E:Z=2.5:1). 1 HNMR (400MHz, CDCl 3 )δ 7.65(d,J=8.0Hz,2.5H),7.30-7.27(m,12.6H),7.24-6.91(m,51.9H),6.87(d,J=16.4Hz,2.5H),6.81( d,J=8.4Hz,5.0H),6.72(d,J=8.4Hz,2.1H),6.60(d,J=16.4Hz,2.5H),6.31(d,J=12.0Hz,1.0H), 6.09(d,J=12.4Hz,1.0H),3.78(s,...

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Abstract

The invention discloses a synthesis method of a bidentate phosphorene ligand, and belongs to the technical field of organic chemistry. Biaryl-2-(disubstituent) phosphine 1 and an alkenyl bromide 2 areadopted as raw materials, and react in an organic solvent at 40-180 DEG C in the presence of a ruthenium catalyst, a ligand and an alkali to obtain the bidentate phosphorene ligand 2-(disubstituent)phosphine-2'-olefin 3. The synthesis steps are simple, and the method can be completed only through one step, active functional groups or complex reaction steps do not need to be introduced to construct C-C bonds in the synthesis process, the synthesis process is efficient, and the operation process is simple; and raw materials are cheap and easy to obtain, the product yield reaches 93%, the requirement for process equipment is low, the reaction process is more environmentally friendly, and potential large-scale industrial production and application prospects are achieved.

Description

technical field [0001] The invention relates to a method for synthesizing a bidentate phosphine ligand, more specifically to a serial method for synthesizing a bidentate phosphine ligand through transition metal catalyzed alkenylation modification of a monophosphine ligand, which belongs to the technical field of organic chemistry. Background technique [0002] Bidentate phosphine ligands, as high-efficiency bidentate ligands, are widely used in transition metal-catalyzed coupling reactions, which play an extremely important role in increasing reaction yield, catalyst activity, regioselectivity and enantioselectivity. . In recent years, transition metal-catalyzed coupling reactions have developed rapidly, and the development of bidentate phosphine ligands has attracted increasing attention. [0003] The synthesis of bidentate phosphine ligands has been reported in some literatures, mainly including the use of highly active alkenyl potassium fluoroborate reagents and metal c...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/50C07F9/58C07F9/655C07F9/6553
CPCC07F9/5022C07F9/5054C07F9/58C07F9/65515C07F9/655345
Inventor 刘悦进
Owner HUBEI UNIV
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