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Palladium catalyst of axis chiral dinaphthalene frame phosphine-containing ligand, synthetic method and use thereof

A technology of phosphine ligands and axial chirality, which is applied in the field of cyclopalladium catalysts, synthesis and application of phosphine-containing ligands with axial chiral binaphthyl skeletons, and can solve the limitations of substrates and reagents. Difficult to prepare, unstable zinc reagent and other problems

Inactive Publication Date: 2008-11-19
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Many research groups are committed to this work, and the reports of asymmetric ring opening have also achieved good results. However, due to the instability of the Grignard reagents, tin reagents, zirconium reagents, and zinc reagents used, they are not easy to prepare or the ligands used in them are relatively Difficult to prepare, and there are limitations in substrates and reagents or complex experimental operating conditions

Method used

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  • Palladium catalyst of axis chiral dinaphthalene frame phosphine-containing ligand, synthetic method and use thereof
  • Palladium catalyst of axis chiral dinaphthalene frame phosphine-containing ligand, synthetic method and use thereof
  • Palladium catalyst of axis chiral dinaphthalene frame phosphine-containing ligand, synthetic method and use thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] Example 1: Synthesis of a cyclopalladium catalyst with an axial chiral binaphthalene skeleton containing a phosphine ligand

[0043]

[0044] Under the protection of argon at 50℃, Pd(OAc) 2 0.30mmol, ligand 0.30mmol, dissolved in 5mL toluene (Tolunene), TLC tracked after 2h until the ligand disappeared. Recrystallized to obtain a yellow-white solid.

[0045] Cat-1 (Ar 1 =Ph): Yield 92%.[a] D 20 =-159°C (c=0.75, CHCl 3 ); M.p.222-228°C; 1 HNMR (300MHz, CDCl 3): δ1.80(s, 3H), 6.45-7.22(m, 11H), 7.23-8.15(m, 11H); 13 CNMR (75MHz, CDCl 3 )δ23.50, 125.01, 126.10, 126.30, 127.20, 128.31, 128.72, 128.84, 131.60, 133.12, 133.70, 134.22, 134.38, 136.01, 136.29, 137.45, 141.30, 176.0 31 P NMR (300MHz, CDCl 3 ): δ35.6; IR(KBr): 3051, 1559, 1436, 1100, 743, 693cm -1 ; MS (ESI) m / z (relative intensity): 625 (M + +Na); HRMS for C 34 h 25 o 2 PPdNa + : theoretical value (Calc) 625.0524; measured value (Found).625.0519.Cat-2 (Ar 1 =p-MeOC 6 h 4 ): Yield 88%.[a] D...

Embodiment 2

[0049] Example 2: Cyclopalladium catalyst asymmetrically catalyzes the ring-opening reaction of organoboron reagents to heteroatom norbornadiene at 0°C.

[0050]

[0051] Add 0.006mmol of cyclopalladium catalyst Cat, 0.2mmol of benzoxa substrate, 0.3mmol of arylboronic acid into the reaction tube, add 0.1mmol of Cs into 3ml of chloroform, and add 0.1mmol of Cs at 0°C 2 CO 3 Aqueous solution; keep stirring at 0°C for 1-24h, then separate by column chromatography, eluent: (V) petroleum ether / (V) ethyl acetate = 10 / 1. The resulting oil was used for further analysis, and the ee% of the product was obtained by HPLC.

[0052] 3aa: oil, 42mg, 95% yield, ee value determined by chiral HPLC. (OD column flow rate, 1.0mL / min, n-hexane / i-PrOH=90 / 10, λ=254nm, t R =8.1min, 12.5min, ee: 79%); 1 H NMR (300MHz, CDCl 3 ): δ3.86-3.92 (m, 1H), 4.90 (t, J = 6.9Hz, 1H), 6.13 (dd, J = 3.9Hz, 9.6Hz, 1H), 6.71 (dd, J = 1.8Hz, 9.9 Hz, 1H), 7.17 (dd, J=1.5Hz, 7.2Hz, 1H), 7.23-7.38 (m, 8H); MS (E...

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Abstract

The invention comprises a cyclopalladated catalyst with axial chiral binaphthyl backbone containing phosphine ligand as well as the synthesis thereof, and the application of the catalyst with cyclopalladated catalyst with axial chiral binaphthyl backbone containing phosphine ligand with a similar structure to the hetero atom norbornadiene ring cleavage reaction through an asymmetric catalytic organic boron agent. The cyclopalladated catalyst containing axial chiral binaphthyl backbone has the following structural formula. The complex is applied to the ring cleavage reaction of various organic boron agents to the hetero atom norbornadiene.

Description

technical field [0001] The present invention includes a class of cyclopalladium catalysts with axchiral binaphthyl skeleton phosphine-containing ligands and their synthesis, and their asymmetric catalytic organic Application of boron reagents to the ring-opening reaction of heteroatom norbornadiene. This type of cyclopalladium catalyst contains an axial chiral binaphthyl skeleton and has the following structural formula: Background technique [0002] Cyclopalladium catalysts with axiral chiral binaphthalene skeletons containing phosphine ligands with similar structures can asymmetrically catalyze the ring-opening reaction of organoboron reagents on heteroatom norbornadiene, and it is easy to obtain a substituted bis Derivatives of hydronaphthol can be easily converted into derivatives of dihydronaphthalene or tetrahydronaphthalene. The skeleton of this dihydronaphthalene or tetrahydronaphthalene exists in many drug molecules and is an important physiologically active unit...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/24C07B53/00
Inventor 侯雪龙莫冬亮张廷珂戴立信
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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