Spiroketal frame bidentate phosphoramidite ligand as well as preparation method and application thereof

A technology of bidentate phosphoramidites and spiroketals, which is applied in the field of bidentate phosphoramidite ligands and their preparation, and can solve the problems of unseen preparation methods and application research reports

Active Publication Date: 2015-07-08
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Abstract
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Problems solved by technology

[0003] Although after more than ten years of development, the synthesis and application of phosphoramidite ligands has become a very important and active research branch in the field of asymmetric catalysis. There are dozens of phosphoramidite ligands with different structures in multiple types of ring and other skeletons, and good research results have been obtained in asymmetric catalysis, especially in conjugate addition, allyl substitution and hydrogenation, but have not been seen so far Related research reports on bidentate phosphoramidite ligands with spiroketal skeleton and their preparation methods and applications

Method used

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  • Spiroketal frame bidentate phosphoramidite ligand as well as preparation method and application thereof
  • Spiroketal frame bidentate phosphoramidite ligand as well as preparation method and application thereof
  • Spiroketal frame bidentate phosphoramidite ligand as well as preparation method and application thereof

Examples

Experimental program
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Effect test

preparation example Construction

[0053] 1) Diphenol preparation of

[0054] Under argon atmosphere, add to the reaction flask (358mg, 1.0mmol) and CH 2 Cl 2 (5mL), the mixture was cooled to -78°C; after stirring for ten minutes, BBr was added dropwise to the reaction system 3 / CH 2 Cl 2 (4.8mmol), reacted for 1 hour, warmed up to room temperature and stirred for half an hour; added water (1mL) to quench the reaction, added CH 2 Cl 2 (3 x 5 mL) extraction; collect CH 2 Cl 2 The solution was rotary evaporated and passed through the column to obtain 227 mg of white solid (80% yield).

[0055] EA / PE(v / v=1 / 5) as the eluent; M.P.175℃; 1 H NMR (CDCl 3 ,400MHz):δ6.83-6.73(m,4H),6.68-6.65(m,2H),5.20(s,2H),3.22-3.10(m,2H),2.83-2.77(m,2H),2.32 -2.27(m,2H),2.03(td,J=16.8,7.6Hz,2H)ppm; 13 C NMR (CDCl 3 ,100MHz):δ144.6,138.9,121.8,121.3,120.1,113.0,97.3,31.1,20.6ppm; FTIR(neat):1587,1475,1378,1285,1215,929,725cm -1 ; EI-MS (70eV) m / z: 284 (M + ); Anal.calcd.for C 17 h 16 o 4 : C, 71.82; H, 5.67%; Found...

Embodiment 1

[0084] Embodiment 1: prepare the bidentate phosphoramidite ligand-1 of spiroketal skeleton

[0085]

[0086] Under argon atmosphere, add dipyrrole phosphorus chloride (190.6mg, 0.96mmol) and anhydrous tetrahydrofuran (2mL) respectively into a 20mL Schlenk tube, cool to 0°C, add dropwise (91mg, 0.32mmol) and anhydrous triethylamine (0.26mL, 1.92mmol) in anhydrous tetrahydrofuran (3mL) solution, slowly warming up to room temperature and stirring overnight, stop the reaction, spin off the solvent under reduced pressure, column chromatography (leaching Lotion: ethyl acetate: petroleum ether = 1 / 10) to obtain 125 mg of white solid, that is, the bidentate phosphoramidite ligand-1 with a spiroketal skeleton, with a yield of 64%; M.P. 129°C.

[0087] 1 H NMR (CDCl 3 ,400MHz):δ6.88-6.76(m,12H),6.61(d,J=8.0Hz,2H),6.29-6.26(m,8H),2.92-2.85(m,2H),2.66(dd,J =17.6,5.2Hz,2H),2.24-2.18(m,2H),2.01(td,J=13.6,6.8Hz,2H)ppm; 13 C NMR (CDCl 3 ,100MHz):δ143.54(d,J=0.8Hz),143.51(d,J=1.6Hz),1...

Embodiment 2

[0088] Embodiment 2: prepare the bidentate phosphoramidite ligand-2 of spiroketal skeleton

[0089]

[0090] Under argon atmosphere, add dipyrrole phosphorus chloride (190.6mg, 0.96mmol) and anhydrous tetrahydrofuran (2mL) respectively into a 20mL Schlenk tube, cool to 0°C, add dropwise (100mg, 0.32mmol) and anhydrous triethylamine (0.26mL, 1.92mmol) in anhydrous tetrahydrofuran (3mL) solution, slowly warming up to room temperature and stirring overnight, stop the reaction, spin off the solvent under reduced pressure, column chromatography (leaching Lotion: ethyl acetate: petroleum ether = 1 / 10) to obtain 191 mg of white solid, which is the bidentate phosphoramidite ligand-2 of spiroketal skeleton, with a yield of 94%; M.P. 115°C.

[0091] 1 H NMR (CDCl 3 ,400MHz):δ6.92-6.84(m,4H),6.77-6.76(m,6H),6.68-6.66(m,4H),6.17-6.15(m,8H),2.89(dd,J=16.0, 6.8Hz,2H),2.53(dd,J=16.0,7.6Hz,2H),2.33-2.29(m,2H),1.91-1.88(m,2H),1.44-1.41(m,2H)ppm; 13 C NMR (CDCl 3 ,100MHz):δ144.0(d,J=2....

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Abstract

The invention discloses a spiroketal frame bidentate phosphoramidite ligand as well as a preparation method and an application thereof. The ligand is the compound shown in a formula I or II or the enantiomer, racemate or diastereoisomer of the compound; and the ligand is prepared by condensation reaction of the compound in the formula I or II, and phosphorus-chlorine compounds. The spiroketal frame bidentate phosphoramidite ligand disclosed by the invention and transition metal salt form a complex, and the complex can be used for terminal olefine hydroformylation or isomerization-hydroformylation of internal olefins; and moreover, the spiroketal frame bidentate phosphoramidite ligand has high catalytic rate, good selectivity and practical value.

Description

technical field [0001] The present invention relates to a class of bidentate phosphoramidite ligands and their preparation methods and applications. Specifically, they relate to a class of bidentate phosphoramidite ligands with a spiroketal skeleton and their preparation methods and applications, belonging to the technical field of organic chemistry . Background technique [0002] Phosphorus ligands are the most studied and widely used ligands so far. According to the different atoms connected to P, phosphorus ligands can be divided into phosphine ligands in which P is connected to three carbon atoms, P and one or more O Atom-linked phosphite ligands and phosphoramidite ligands containing P linked to one or more N atoms. Phosphoramidite ligands have been developed rapidly in the past ten years due to their stable structure, simple synthesis, easy modification, and unique effects. Infused with new vitality. The phosphoramidite ligand structure can be divided into two parts...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/6561B01J31/22C07C45/50C07C47/02
Inventor 丁奎岭王正贾肖飞
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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