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New type spirocyclic phosphic ester, preparation method and application in asymmetric addition reaction

A technology of spirocyclic phosphite and aryl phosphite, which is applied in the field of novel chiral spirocyclic monophosphorous ligands, can solve the problems of low enantioselectivity and inability to obtain ideal results, and achieve a simple and efficient synthesis method. The effect of convenient group construction and high stereoselectivity

Inactive Publication Date: 2006-04-19
NANKAI UNIV
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AI Technical Summary

Problems solved by technology

[0003] As far as the Rh(I)-catalyzed asymmetric addition of boronic acid to aldehydes and imines is concerned, although people have done a lot of research work, the use of existing single phosphorus ligands still cannot obtain ideal results, mainly as Low enantioselectivity (Sakai, M.; Ueda, M.; Miyaura, N. Angew. Chem. Int. Ed. 1998, 37, 3279), or better results can only be obtained for specific types of substrates ( Kuriyama, M.; Soeta, T.; X.-Y., Hao; Q. Chen, Tomioka, K.J, Am, Chem.Soc.2004, 126, 8128)

Method used

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  • New type spirocyclic phosphic ester, preparation method and application in asymmetric addition reaction
  • New type spirocyclic phosphic ester, preparation method and application in asymmetric addition reaction
  • New type spirocyclic phosphic ester, preparation method and application in asymmetric addition reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] Example 1: Preparation of (R)-O, O'-[7,7'-(1,1'-spirodihydroindene)]-O-methyl phosphite

[0039]

[0040] Under a nitrogen atmosphere, add 263 mg (2.6 mmol) triethylamine to a reaction flask containing 308 mg (1.2 mmol) (R)-spirocyclic diphenol and 15 mL of dichloromethane, and add 263 mg (2.6 mmol) of triethylamine to the reaction flask at 0°C under stirring. 174 mg (1.3 mmol) of methoxyphosphorus dichloride was added dropwise, and the reaction was maintained at 0° C. for 0.5 hours, and then reacted at room temperature for 3 hours. The obtained reaction solution was desolventized under reduced pressure, and the residue was dissolved in n-hexane, filtered through diatomaceous earth, and 318 mg of white solid was obtained after desolventization. Yield: 85%. Melting point: 135-137°C. [α] D 20 =-522.8 (c 0.5, CH 2 Cl 2 ); 1 H NMR: δ7.21-7.14 (m, 2H, Ar-H), 7.06 (t, J=8Hz, 2H, Ar-H), 6.92 (d, J=7.8Hz, 1H, Ar-H), 6.78 (d, J=7.8Hz, 1H, Ar-H), 3.46 (d, J=10.1Hz, 3H,...

Embodiment 2

[0041] Example 2: Preparation of (R)-O, O'-[7,7'-(1,1'-spirodihydroindane)-O-phenyl phosphite

[0042]

[0043] Under a nitrogen atmosphere, add 263 mg (2.6 mmol) of triethylamine to a reaction flask containing 308 mg (1.2 mmol) (R)-spirocyclic diphenol and 15 mL of toluene, and dropwise add Phosphorus trichloride 178mg (1.3mmol), then react at room temperature for 20 hours, filter through diatomaceous earth, add 113mg (1.2mmol) of phenol to the obtained filtrate, add triethylamine 152mg (1.5mmol) under stirring, and react at room temperature After 3 hours, the solvent was removed, and the residue was subjected to silica gel column chromatography (eluent: ethyl acetate / petroleum ether=1:10) to obtain 336 mg of a white solid. Yield: 75%. The melting point is 104-105°C. [α] D 25 =+72(c 0.5, CHCl 3 ). 1 H NMR: δ7.35-6.77(m, 11H), 3.12-3.03(m, 2H), 2.87-2.80(m, 2H), 2.28-2.22(m, 2H), 2.07-2.00(m, 2H). 13 C NMR: δ151.2, 145.1, 144.7, 143.8, 142.3, 141.9, 138.7, 128.7, 127...

Embodiment 3

[0044] Example 3: Preparation of (R)-O, O'-[7,7'-(1,1'-spirodihydroindene)]-O-tert-butyl phosphite

[0045] The phenol in Example 2 was replaced with tert-butanol, and the preparation method was the same as in Example 2 to obtain (R)-O, O'-[7,7'-(1,1'-spirodihydroindene)]-O - tert-butyl phosphite, white solid, yield: 65%. Melting point: 57-58°C. [α] D 20 =+80(c0.5, CHCl 3 ). 1 H NMR: δ7.20-6.76(m, 6H), 3.08-3.02(m, 2H), 2.85-2.81(m, 2H), 2.24-2.18(m, 2H), 2.04-2.00(m, 2H), 1.48(s, 9H). 13 C NMR: δ145.1, 14.8, 144.4, 142.9, 142.0, 139.1, 127.3, 126.2, 121.8, 120.8, 120.5, 119.9, 58.0, 37.4, 36.9, 29.9 9.5. 31 P NMR: δ128.1.HR-MS (FAB) (theoretical) C 21 h 23 o 3 P+H: 355.1463 (355.1457).

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Abstract

A spirocyclosulphite is prepared from spirocyclodiphenol through three methods. Its spirodihydroindene structure has axial chirality, so said compound has two mutamers: levo- and dextro- spirocyclosulphite compounds. It can be used for the asymmetrical addition reaction of aldehyde and imine with high stereo activity.

Description

technical field [0001] The present invention relates to a novel chiral spirocyclic monophosphorus ligand, specifically a C 2 Spiral phosphite with symmetrical axis and its preparation method, and its application in the asymmetric addition reaction of aldehydes and imines. Background technique [0002] Phosphorus-containing chiral ligands play an important role in asymmetric catalytic reactions, and they exhibit excellent chirality-inducing abilities in many transition metal-catalyzed reactions (Ohkuma, T.; Kitamura, M.; Noyori, R. Catalytic Asymmetric Synthesis, Wiley, New York, 2000). Most of the currently reported phosphorus-containing chiral ligands are bidentate ligands, such as DIOP, DIPAMP, BINAP, DuPhos, etc., and their successful application in asymmetric catalytic reactions has made monodentate phosphorus ligands The study of the body was neglected until 1991 when Hayashi et al. successfully applied the monodentate MOP ligand to the Pd-catalyzed allyl substitution...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/145
Inventor 周其林段海峰史文健王立新谢建华
Owner NANKAI UNIV
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