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Allylated monophosphine ligand and preparation method thereof

A technology of allylation mono- and allylation, which is applied in the field of new allylation monophosphine ligands and its preparation, can solve the problems of limiting biphenyl monophosphine ligands, and achieve low environmental pollution impact, Synthetic process is efficient and the effect of reducing production costs

Pending Publication Date: 2022-05-13
HUBEI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The modification of new monophosphine ligands in the prior art still has limitations, which limits the development of biphenyl monophosphine ligands. It is necessary to develop new functionalized monophosphine ligands to enrich the library of phosphine ligands

Method used

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  • Allylated monophosphine ligand and preparation method thereof
  • Allylated monophosphine ligand and preparation method thereof
  • Allylated monophosphine ligand and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] The novel allylated monophosphine ligand {(E)-2-((2'-(diphenylphosphino)-[1,1'-biphenyl]-2-yl)methyl)- 3-ethyl phenylacrylate}, the synthetic route is as follows:

[0027]

[0028] Add 33.8 mg (0.1 mmol) of 2-diphenylphosphine-biphenyl 1a, 49.6 mg of ethyl 2-(acetoxyphenylmethyl)acrylate 2a (0.2 mmol), 3.1 mg of p-cymene to the reaction kettle Ruthenium dichloride dimer, 7.3mg 1-tert-butoxycarbonamide cyclohexanecarboxylic acid, 1.8mg tris(4-methoxyphenyl) phosphine, 32.8mg sodium phosphate and 1.5mL n-hexane, after mixing evenly Pass argon into the reaction system, control the reaction in an argon atmosphere, and react at 120°C for 12 hours, then cool to room temperature, filter with diatomaceous earth, and distill under reduced pressure to obtain 39.5 mg of product 3a by column chromatography. rate of 75%. 1 H NMR (400MHz, CDCl 3 )δ7.96(s,1H),7.43-7.36(m,3H),7.35-7.26(m,7H),7.26-7.16(m,8H),7.10-6.97(m,4H),6.72(d, J=8.0Hz, 1H), 4.25-4.18(m, 2H), 3.80(q, J=32.0Hz...

Embodiment 2

[0036] In this example, the novel alkylated monophosphine ligand {3-(2'-(diphenylphosphino)-[1,1'-biphenyl]-2-yl) tert-butyl propionate}, synthetic route as follows:

[0037]

[0038] Added 37.2 mg (0.1 mmol) 4-chloro-2-diphenylphosphine-biphenyl 1b, 49.6 mg ethyl 2-(acetoxyphenylmethyl)acrylate 2a (0.2 mmol), 3.1 mg to the kettle p-cymene dichloride ruthenium dimer, 7.3 mg 1-tert-butoxycarbonamide cyclohexanecarboxylic acid, 1.8 mg tris(4-methoxyphenyl) phosphine, 32.8 mg sodium phosphate and 1.5 mL n-hexane, stirred After mixing evenly, pass argon into the reaction system, control the reaction in an argon atmosphere, and react at a temperature of 120°C for 12 hours, then cool to room temperature, filter with diatomaceous earth, and separate by column chromatography after vacuum distillation to obtain 50.4 mg of the product 3b, yield 90%. 1 H NMR (400MHz, CDCl3) δ7.96(s, 1H), 7.40-7.27(m, 9H), 7.26-7.13(m, 8H), 7.09-6.97(m, 3H), 6.93(dd, J=8.0 ,4.0Hz,1H),6.59(d,J=12.0Hz...

Embodiment 3

[0040] The novel alkylated monophosphine ligand (E)-2-((2'-(diphenylphosphino)-4'-methyl-[1,1'-biphenyl]-2-yl) in this example Methyl)-3-ethyl phenylacrylate, the synthetic route is as follows:

[0041]

[0042] Add 35.2 mg (0.1 mmol) (4-methyl-[1,1'-biphenyl]-2-yl) diphenylphosphine 1c, 49.6 mg 2-(acetoxyphenylmethyl) to the reaction kettle Ethyl acrylate 2a (0.2 mmol), 3.1 mg p-cymene dichloride ruthenium dimer, 7.3 mg 1-tert-butoxycarbonamide cyclohexanecarboxylic acid, 1.8 mg tris(4-methoxyphenyl)phosphine , 32.8mg of sodium phosphate and 1.5mL of n-hexane, stirred and mixed evenly, then passed argon into the reaction system, controlled the reaction in an argon atmosphere, and the temperature was 120°C for 12 hours, then cooled to room temperature, filtered with diatomaceous earth, After distillation under reduced pressure, 14.1 mg of product 3c was obtained by column chromatography, with a yield of 26%. 1 HNMR (400MHz, CDCl 3 )δ7.94(s,1H),7.40-7.36(m,2H),7.33-7.16(m...

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Abstract

The invention relates to an allylated monophosphine ligand and a preparation method thereof, and belongs to the technical field of organic chemistry. A compound 1 and a compound 2 are used as raw materials and react in an inert atmosphere at 60-140 DEG C in the presence of a ruthenium catalyst, a ligand, alkali, an additive and an organic solvent, and the novel allylated monophosphine ligand is prepared after treatment. The preparation method disclosed by the invention is simple in synthesis step, can be completed by only one step, has the advantages of easily available raw materials, simple and convenient process operation, high efficiency, rapidness, reduction of production cost and requirements on equipment and the like, is high in product yield, and is easy to realize industrial large-scale production.

Description

technical field [0001] The invention belongs to the technical field of organic chemistry, and in particular relates to a novel allylated monophosphine ligand and a preparation method thereof. Background technique [0002] Phosphine ligands are the most widely used ligands in transition metal-catalyzed cross-coupling reactions, which play a key role in improving catalyst activity, reaction yield, regioselectivity and enantioselectivity. Among them, biphenyl monophosphine ligands have attracted much attention due to their strong power supply and large steric effect. At present, biphenyl monophosphine ligands have achieved a series of functionalization, including alkylation, alkenylation, arylation, boronation, etc. [0003] The literature (Angew.Chem.Int.Ed.2019, 58, 14110) reported that expensive Rh was used as a metal catalyst and olefin was used as a coupling reagent to realize the ortho-alkylation of biarylphosphine through C-H activation. The literature (Nat Commun. 201...

Claims

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Application Information

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IPC IPC(8): C07F9/50C07F9/572
CPCC07F9/5054C07F9/572
Inventor 刘悦进王中慧张琪曾明华
Owner HUBEI UNIV
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