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Chiral spiro phosphoramide derivative and preparation method thereof

A technology for spirocyclic phosphonamide and derivatives, which is applied in the field of chiral spirocyclic phosphonamide derivatives and their preparation, can solve the problems of limited types of chiral phosphonamide derivatives and the like, and achieves wide range of catalytic organic reactions and good activity and the effect of enantioselectivity

Inactive Publication Date: 2012-06-27
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] But so far, the reported chiral phosphonamide derivatives are limited

Method used

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  • Chiral spiro phosphoramide derivative and preparation method thereof
  • Chiral spiro phosphoramide derivative and preparation method thereof
  • Chiral spiro phosphoramide derivative and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Example 1 ( S Preparation of )-O,O'-{7,7'-[6,6'-bis-(1-naphthyl)-1,1'-spirobisdihydroindane]}phosphoramide

[0022] The structural formula is as follows:

[0023]

[0024] put the compound ( S )-6,6'-bis-(1-naphthyl)-1,1'-spiroindane-7,7'-diol (10 mmol), phosphorus oxychloride and 4-N-bis The molar equivalent ratio of methylamino and triethylamine is 1:1~1.5:2:5~10 mixed in 30 ml of dichloromethane solvent, at 0-5 o After C reacted for 3 hours, 20 mmoles of trifluoromethanesulfonamide and 15 milliliters of propionitrile were added; o C reaction for 6 hours, cooling to end the reaction, then adding water and dichloromethane to extract, the organic phase was washed with dilute hydrochloric acid and saturated brine in turn, then dried with sodium sulfate, filtered, the filtrate was concentrated to dryness under reduced pressure, and then passed through column chromatography A solid was obtained, which was dissolved in dichloromethane, washed with dilute hydrochlor...

Embodiment 2

[0025] Example 2 ( S Preparation of )-O,O'-{7,7'-[6,6'-bis-(1-naphthyl)-1,1'-spirobisdihydroindene]}thiophosphoramide

[0026] The structural formula is as follows:

[0027]

[0028] put the compound ( S )-6,6'-di-(1-naphthyl)-1,1'-spiroindane-7,7'-diol (10 mmol), phosphorus tribromide and triethylamine in moles The equivalent ratio is 1:1.2:10 mixed in 40 ml of toluene solvent, at 35 o After C reacted for 3 hours, 30 mmol of trifluoromethanesulfonamide was added; o C reaction for 6 hours, then add 20 mmol of sulfur powder, react at 110 degrees for 24 hours; then cool to end the reaction, add water and dichloromethane for extraction, the organic phase is washed with dilute hydrochloric acid and saturated saline successively, and then washed with sodium sulfate Drying, filtration, the filtrate was concentrated to dryness under reduced pressure, and then obtained a solid by column chromatography, the gained solid was dissolved in dichloromethane, washed with dilute hydr...

Embodiment 3

[0029] Embodiment 3 ( S )-O, O'-{7,7'-[6,6'-two-(1-naphthyl)-1,1'-spirobisdihydroindane]} phosphorothioate preparation, the structural formula is as follows:

[0030]

[0031] put the compound ( S )-6,6'-di-(1-naphthyl)-1,1'-spiro indane-7,7'-diphenol (10 mmol), phosphorus pentasulfide in a molar equivalent ratio of 1:0.5 In 40 ml of xylene solvent, at 120 o C reacted for 5 hours, cooled to end the reaction, then added water and dichloromethane to extract, the organic phase was washed with dilute hydrochloric acid and saturated brine in turn, then dried with sodium sulfate, filtered, the filtrate was concentrated to dryness under reduced pressure, and then passed through the column layer The obtained solid was dissolved in dichloromethane, washed with dilute hydrochloric acid, then the organic phase was concentrated under reduced pressure, and vacuum-dried to obtain ( S )-O,O'-{7,7'-[6,6'-di-(1-naphthyl)-1,1'-spirobisdihydroindene]}thiophosphoric acid, code name is Cata...

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Abstract

The invention discloses a chiral spiro phosphoramide derivative, which is a compound with a structural formula (1), a racemate or an optical isomer thereof. The chiral spiro phosphoramide derivative has a chiral spirobiindane skeleton, and is synthesized by adopting a 1,1'-spiro indane-7,7'-diphenol derivative with a spiro skeleton and a characteristics of optical activity as a chiral starting raw material. The chiral spiro phosphoramide derivative is a novel Bronsted acid organic small molecule catalyst, and can be widely used for catalysis of a plurality of asymmetric organic reactions.

Description

technical field [0001] The invention relates to a chiral spirocyclic phosphonamide derivative and a preparation method thereof. Background technique [0002] Asymmetric catalysis is an important field in chemical research, and many chiral compounds produced by this technology can become chiral drugs or chiral pesticides. Nowadays, asymmetric reactions using small organic molecules as catalysts have become a new frontier in organic asymmetric synthetic chemistry. In 2004, Terada and Akiyama firstly reported the application of axial chiral binaphthyl phosphate compounds to asymmetric catalytic reactions [(a) Akiyama, T.; Itoh, J.; Yokota, K.; Fuchibe, K. Angew. Chem. Int. Ed. 2004, 43 , 1566. (b) Uraguchi, D.; Terada, M. J. Am. Chem. Soc. 2004, 126 , 5356. ], and derived chiral binaphthylphosphonamide derivatives and their salts are widely used in a variety of asymmetric organic synthesis [Terada, M. Synthesis 2010, 12 , 1929; M. S. Taylor, E. N. Jacobsen, Angew. Che...

Claims

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Application Information

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IPC IPC(8): C07F9/6574B01J31/02C07D209/14
Inventor 林旭锋赵彦彦屈海军李雪健
Owner ZHEJIANG UNIV
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