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Chiral spiro-phosphate and preparation method and application thereof

A spirocyclic phosphoric acid and chiral technology, which is applied in the field of chiral spirocyclic phosphoric acid and its preparation and application, can solve the problems of limited types of chiral phosphoric acid catalysts, and achieve good activity and enantioselectivity

Active Publication Date: 2011-04-27
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But so far, the reported chiral phosphoric acid catalysts are limited

Method used

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  • Chiral spiro-phosphate and preparation method and application thereof
  • Chiral spiro-phosphate and preparation method and application thereof
  • Chiral spiro-phosphate and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Example 1 Preparation of (S)-O,O'-{7,7'-[6,6'-bis-(1-naphthyl)-1,1'-spirodihydroindene]} phosphoric acid The structural formula is as follows :

[0029]

[0030] In the first step, 10 millimoles of (S)-1,1'-spiroindan-7,7'-diphenol and 30 millimoles of sodium hydride (60% content stored in mineral oil) are mixed in 100 ml In tetrahydrofuran, then 25 millimoles of chloromethyl methyl ether was added dropwise to the above reaction solution within 30 minutes at a temperature of 0°C and reacted at room temperature for 12 hours after the drop was completed. After the reaction was completed, 200 ml of water and 500 ml were added. Ethyl acetate, the organic phase was washed with 500 ml of saturated brine, dried over anhydrous sodium sulfate, filtered to remove sodium sulfate, and the filtrate was concentrated under reduced pressure to dryness to obtain a quantitative compound C;

[0031] In the second step, under the protection of nitrogen, mix 10 millimoles of compound C and 20 m...

Embodiment 2

[0034] Example 2 Preparation of various chiral spirocyclic phosphates

[0035] The preparation process is the same as in Example 1, but 1-naphthylboronic acid is replaced by phenylboronic acid, p-chlorophenylboronic acid, biphenylboronic acid or 3,5-ditrifluoromethylphenylboronic acid. The physical data of the corresponding chiral spirocyclic phosphate are as follows:

[0036] (S)-O,O’-{7,7’-[6,6’-diphenyl-1,1’-spirodihydroindene]} phosphoric acid

[0037]

[0038] The yield was 88%.

[0039] Melting point is greater than 300℃; [α] D 20 = -513.2 (c = 0.50, MeOH). 1 H NMR(400MHz, DMSO-d 6 )δ1.88-1.95(m, 2H), 2.18-2.22(m, 2H), 2.75-2.81(m, 2H), 3.01-3.10(m, 2H), 7.01(d, J=7.2Hz, 2H) , 7.10 (d, J = 7.6 Hz, 2H), 7.19 (t, J = 7.2 Hz, 2H), 7.28 (t, J = 7.6 Hz, 4H), 7.59 (d, J = 7.6 Hz, 4H); 13 C NMR(100MHz, DMSO-d 6 )δ30.0, 39.0, 59.5, 120.1, 126.3, 127.9, 129.7, 130.0, 134.6, 140.2, 142.0, 144.2, 146.3; 31 P NMR(202MHz, DMSO-d 6 )δ-11.0; HRMS(ESI)calcd for C 29 H 22 O 4 P - ([M-H] - ): 46...

Embodiment 3

[0052] Example 3 Chiral spirocyclic phosphoric acid catalyzes the reaction of indole compounds with sulfonimide derivatives

[0053] Combine 1 mmol sulfonimide derivative G, 5 mmol indole derivative F, and 0.1 mmol (S)-O,O'-{7,7'-[6,6'-bis-(1- Naphthyl)-1,1'-spirodihydroindene]} phosphoric acid was mixed in 5 ml of toluene solvent, reacted at -60°C for a certain period of time (see Table 1), and then sodium hydroxide solution was added to neutralize the reaction. It was extracted with ethyl acetate, washed with saturated brine, dried over sodium sulfate, filtered, and the filtrate was concentrated to dryness under reduced pressure, and then the chiral 3-alkylated indole derivative H was obtained by column chromatography. The optical purity of the product was determined by HPLC. The results are shown in Table 1.

[0054]

[0055] The structural formula of the catalyst spirocyclic phosphoric acid A here is:

[0056]

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Abstract

The invention relates to a chiral spiro-phosphate and a preparation method and application thereof. The chiral spiro-phosphate compound has a structure of a formula (1) and has the main structural characteristic of chiral spiral dihydroindene skeleton. The chiral spiro-phosphate compound can be synthesized by using 1,1'-spiro-dihydroindene-7,7'-diphenol with spiral skeleton and optical activity as a chiral initial raw material. The chiral spiro-phosphate is a novel protonic acid organic small molecular catalyst, can be widely applied in various catalytic asymmetric organic reactions, particularly can be applied in asymmetrical catalytic reaction of indole alkylation, and has and high enantiomer selectivity, the reaction condition is mild , and the yield is good.

Description

Technical field [0001] The invention relates to a novel chiral spirocyclic phosphoric acid catalyst and a preparation method and its application in the asymmetric organic catalytic reaction of indole alkylation. Background technique [0002] Asymmetric catalysis of organic reactions is an important field in chemistry research. Today, the use of small organic molecules as catalysts, that is, asymmetric reactions promoted by organic catalysts, has become a new frontier in synthetic organic chemistry [Dalko, PI; Moisan, L.Angew.Chem.lnt.Ed.Engl.2004, 43 , 5138]. In 2004, Terada and Akiyama respectively reported for the first time the application of axial chiral binaphthyl phosphates to asymmetric catalytic reactions [(a) Akiyama, T.; Itoh, J.; Yokota, K.; Fuchibe, K. Angew. Chem. Int. Ed. 2004, 43, 1566. (b) Uraguchi, D.; Terada, MJAm. Chem. Soc. 2004, 126, 5356. (c) Uraguchi, D.; Sorimachi, K.; Terada, MJAm.Chem.Soc.2004, 126, 11804]. This pioneering work makes chiral phosphoric...

Claims

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Application Information

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IPC IPC(8): C07F9/6574B01J31/02C07D209/14C07D405/06C07B53/00
Inventor 黄丹徐方曦林旭锋王彦广
Owner ZHEJIANG UNIV
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