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Chiral sugar-containing thiosemicarbazide catalyst derived from binaphthalene skeleton and preparation method and application thereof

A technology of thiosemicarbazide and binaphthalene is applied in the preparation of sugar derivatives, chemical instruments and methods, catalysts for physical/chemical processes, etc., and can solve the problems of sometimes poor stereo control and the like

Pending Publication Date: 2021-07-16
TIANJIN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

It should be pointed out that the previously developed thiourea catalysts often only contain one kind of chiral skeleton, and the effect of stereo control is sometimes poor, and there are still few reports on the simultaneous introduction of two or more chiral skeletons into thiourea catalysts. Has a good research and development space

Method used

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  • Chiral sugar-containing thiosemicarbazide catalyst derived from binaphthalene skeleton and preparation method and application thereof
  • Chiral sugar-containing thiosemicarbazide catalyst derived from binaphthalene skeleton and preparation method and application thereof
  • Chiral sugar-containing thiosemicarbazide catalyst derived from binaphthalene skeleton and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Example 1: (D.S.R.R.-binaphthalene-1,2-diphenylethylenediaminetetraacetylglucothiourea) (Catalyst 1)

[0023]

[0024] Step 1: 2,2'-bis(bromomethyl)-1,1'-binaphthyl Ia (969mg, 2.2mmol) containing S configuration, 5-acetyl-1,3-dimethylbaby N,N - Dimethylformamide (12 mL) solution was stirred at 45° C. for 72 hours under argon protection. The reaction was quenched with distilled water (60 mL). The aqueous phase was extracted four times with ethyl acetate (120 mL), the organic phase was washed once with 50 mL of saturated brine, dried by adding anhydrous sodium sulfate, the solvent was removed under reduced pressure, and separated by a neutral alumina column (petroleum ether / ethyl acetate = 6 / 1 as the eluent) to obtain light yellow solid intermediate Ib (1.19g, yield 89%). 1 H NMR (400MHz, CDCl 3 )δ2.44(s,3H),3.27(d,J=12.3Hz,2H),3.31(s,3H),3.45(s,3H),3.90(d,J=12.3Hz,2H),4.16( d,J=5.1Hz,1H),5.30(dd,J=5.1,7.5Hz,1H),7.16-7.43(m,18H),7.82(d,J=8.2Hz,2H),7.89(d,J =8.2Hz...

Embodiment 2

[0027] Example 2: (D.S.S.S-binaphthalene-1,2-diphenylethylenediaminetetraacetylglucothiourea) (catalyst 2)

[0028]

[0029] Step 1: 2,2'-bis(bromomethyl)-1,1'-binaphthyl Ia (969mg, 2.2mmol) containing S configuration, 5-acetyl-1,3-dimethylbaby Diphenylethylenediamine (786mg, 2mmol) and triethylamine (610μl, 4.4mmol) in tetrahydrofuran (12mL) in (1S, 2S) configuration protected by the acid protecting group (DAB) were placed under argon protection in Stir at 50°C for 48 hours. The reaction was quenched with distilled water (60 mL). The aqueous phase was extracted four times with ethyl acetate (120 mL), the organic phase was washed once with 50 mL of saturated brine, dried by adding anhydrous sodium sulfate, the solvent was removed under reduced pressure, and separated by a neutral alumina column (petroleum ether / ethyl acetate = 6 / 1 as the eluent) to obtain light yellow solid intermediate Ib (1.13g, yield 85%). 1 H NMR (400MHz, CDCl 3 )δ2.43(s,3H),3.27(d,J=12.4Hz,2H),3.31...

Embodiment 3

[0032] Example 3: (D.R.R.R-binaphthalene-1,2-diphenylethylenediaminetetraacetylglucothiourea) (catalyst 3)

[0033]

[0034] Step 1: 2,2'-bis(bromomethyl)-1,1'-binaphthyl Ia (969 mg, 2.2 mmol) containing (R) configuration, 5-acetyl-1,3-dimethyl A solution of diphenylethylenediamine (786mg, 2mmol) and DABCO (492mg, 4.4mmol) in (1R, 2R) configuration protected by a barbituric acid protecting group (DAB) in dichloromethane (12mL) was protected under argon. Stir at 50°C for 48 hours. The reaction was quenched with distilled water (60 mL). The aqueous phase was extracted four times with ethyl acetate (120 mL), the organic phase was washed once with 50 mL of saturated brine, dried by adding anhydrous sodium sulfate, the solvent was removed under reduced pressure, and separated by a neutral alumina column (petroleum ether / ethyl acetate = 6 / 1 as the eluent) to obtain light yellow solid intermediate Ib (1.02g, yield 75%). 1 H NMR (400MHz, CDCl 3 )δ2.41(s,3H),3.27(d,J=12.2Hz,2H),...

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Abstract

The invention relates to a chiral sugar-containing thiosemicarbazide catalyst derived from binaphthalene skeleton and a preparation method and application thereof. The preparation method comprises the following steps: carrying out cyclization reaction on S or R configuration 2, 2 '-bis (bromomethyl)-1, 1'-binaphthalene (Ia) and chiral (S, S) configuration or (R, R) configuration 1, 2-diphenylethylenediamine protected by a 5-acetyl-1, 3-dimethyl barbituric acid protecting group in an organic solvent under the action of alkali catalysis to prepare an intermediate (Ib); reacting the intermediate (Ib) in an organic solvent under the action of a strong base to remove a protecting group to prepare an intermediate (Ic), reacting the intermediate (Ic) with sugar with an isothiocyanate group in the organic solvent at a low temperature, and separating and purifying to obtain the chiral sugar-containing thiosemicarbazide (I) derived from the protecting group-removed target binaphthalene skeleton. The catalyst is used for catalyzing an asymmetric decarboxylation Mannich reaction of cyclic imine, and an addition product is prepared with a high yield of 84-97% and a high enantioselectivity ee value of 83-98%.

Description

technical field [0001] The invention relates to a novel chiral sugar-containing thiourea catalyst, and specifically discloses a chiral sugar-containing thiosemicarbazide catalyst derived from a binaphthyl skeleton, a preparation method and an application thereof. Background technique [0002] Chiral thiourea catalysts are a very important class of organic small molecule catalysts, which have been widely used in asymmetric catalytic synthesis. Chiral thiourea catalyst, as a hydrogen bond donor type small molecule catalyst, activates the reaction reagent by forming a hydrogen bond with the substrate to catalyze the reaction, thereby achieving high enantioselective synthesis. Since Jacobsen first applied the thiourea catalyst to the asymmetric Strecker reaction in 1998, new chiral thiourea catalysts have been synthesized and used in different asymmetric synthesis, with good asymmetric catalytic effect. The typical chiral skeletons of thiourea catalysts that have been developed...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/02C07F9/6547C07H13/12C07H1/00
CPCB01J31/0271B01J31/0249C07H13/12C07H1/00C07F9/6547B01J2231/346Y02P20/55
Inventor 张发光王雪琪马军安
Owner TIANJIN UNIV
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