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Imidazole carbene ligand with amide remote basic functional group as well as synthesis method and application thereof

A technology of carbene ligand and synthesis method, which is applied in the directions of organic compound/hydride/coordination complex catalyst, gold organic compound, chemical instrument and method, etc. Obstacles and other problems, to achieve the effect of simple and efficient response

Active Publication Date: 2019-11-22
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Due to the linear nature of the carbene-gold-alkyne complex, there is a steric barrier between the ligand and the nucleophile, and the distance is too far to be regulated
Currently existing carbene gold catalysts do not take this into account and solve this problem

Method used

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  • Imidazole carbene ligand with amide remote basic functional group as well as synthesis method and application thereof
  • Imidazole carbene ligand with amide remote basic functional group as well as synthesis method and application thereof
  • Imidazole carbene ligand with amide remote basic functional group as well as synthesis method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] Imidazole carbene ligand, which is the compound described in formula (1)

[0043]

[0044] The compound is prepared as follows:

[0045] Step 1: Dissolve 3-iodobenzoic acid (A) (10 mmol) in 50 mL of dichloromethane, add oxalyl chloride (2.5 equiv) and 3 drops of N,N-dimethylformamide and stir at room temperature for 4 hours. The mixture was rotovaped and dried in vacuo to give the product 3-iodobenzoyl chloride. Under nitrogen protection, 3-iodobenzoyl chloride was dissolved again in 50 mL of dichloromethane and cooled in an ice bath. Will contain 15mmol tetrahydropyrrole (1.5equiv) and 20mmol Et 3 A solution of N(2 equiv) in 10 mL of dichloromethane was slowly added dropwise, then the reaction mixture was stirred at room temperature. After 1 hour, add 50mL of water and 100mL of dichloromethane, separate and dry the organic phase, spin dry, use a mixed solvent of petroleum ether and ethyl acetate with a volume ratio of 10:1–2:1 as the eluent, and the column Chrom...

Embodiment 2

[0070] Synthesis of Imidazole Carbene Gold Complexes

[0071]

[0072] Under nitrogen protection, add 1 mmol of imidazole carbene ligand with amide remote basic functional group represented by formula (1) into 5 mL of redistilled tetrahydrofuran, and add 1.2 mmol of lithium bistrimethylsilylamide (1.2 equiv) at -78 °C , stirred for half an hour, added 0.95mmol dimethyl sulfide gold chloride (0.95equiv), stirred for 16 hours, spin-dried and passed through the column, and the mixed solution of dichloromethane:methanol with a volume ratio of 40:1-20:1 As the eluent, the eluate containing the target product is collected to obtain the carbene gold catalyst (2).

[0073] Pale yellow solid, yield 50%, detection result is as follows:

[0074] 1 H NMR (500MHz, DMSO) δ8.06(s, 1H), 7.76–7.72(m, 2H), 7.69–7.65(m, 2H), 7.54(t, J=7.7Hz, 1H), 7.16(dd, J=9.2,6.7Hz,1H),7.07(s,2H),6.74(dd,J=6.6,1.1Hz,1H),3.69(dd,J=28.3,6.4Hz,2H),3.45(t,J =6.9Hz, 2H), 2.31(s, 3H), 1.93(d, J=4.9Hz, 6H), 1....

Embodiment 3

[0076] Carbene gold catalyst (2) catalyzes the reaction of phenylacetylene and diphenylphosphonic acid to generate phenyl vinyl ether.

[0077]

[0078] Under nitrogen protection, 0.006mmol carbene gold catalyst (3mol%), 0.012mmol bistrifluoromethanesulfonate imide silver salt (6mol%), 0.2mmol diphenylphosphonic acid, 0.4mmol phenylacetylene in 1,2-dichloro In ethane, react at 50° C. for 12 hours to obtain the phenyl vinyl ether product with a yield of 67%.

[0079]

[0080] Pale yellow solid, the test results are as follows:

[0081] 1 H NMR (500MHz, CDCl3) δ7.93-7.88(m, 4H), 7.61-7.53(m, 4H), 7.49-7.45(m, 4H), 7.38-7.34(m, 3H), 5.23(dd, J =2.8,2.2Hz,1H),5.18(dd,J=2.9,1.9Hz,1H).

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Abstract

The invention discloses an imidazole carbene ligand with an alkaline remote functional group, which is a compound shown as a formula (1). The ligand and gold can form a stable metal complex used for catalyzing cyclization reactions, rearrangement reactions, nucleophilic addition reactions and the like. The invention provides a synthetic route of the novel imidazole carbene ligand and a metal complex thereof, achieving simple and efficient alkyne nucleophilic addition. The NHC-Au catalyst is provided with a Lewis acid activation center taking gold as a center and an alkali activation center taking a basic group as a center, and a hindered Lewis acid-base pair can be formed by utilizing a unique linear structure of a monovalent gold complex (ligand-gold-substrate), so that beneficial interaction between the basic functional group and a nucleophilic reagent or substrate is realized, and dual synergistic activation effects of a catalytic system on a reaction transition state are achieved.

Description

technical field [0001] The invention relates to the technical field of catalysts, in particular to an imidazole carbene ligand with a remote basic functional group, a synthesis method thereof, a metal complex and an application thereof. Background technique [0002] In the past decade, homogeneous gold-catalyzed reactions have developed into an important research field in organic chemistry. Gold catalysts, as a soft Lewis acid, can efficiently activate alkynes, allenes, etc. to generate active gold species, followed by further transformations, which can catalyze cyclization reactions, rearrangement reactions, nucleophilic addition reactions, etc. Imidazole-based N-heterocyclic carbene is a class of general-purpose catalysts in many reactions and can be used as a ligand for transition metal catalysts. At present, the carbene that forms a complex with a metal as a catalyst, in addition to IMesHCl, IPrHCl and other classic carbene, only chiral carbene [Check, C.T, Ferrocene-Ba...

Claims

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Application Information

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IPC IPC(8): C07D471/04C07F1/12B01J31/22C07F9/32
CPCB01J31/2273B01J2231/32B01J2531/18C07D471/04C07F1/12C07F9/3229
Inventor 刘运奎徐勇财周丙伟
Owner ZHEJIANG UNIV OF TECH
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