Chiral phosphorus-sulfur compound and Michael addition method thereof

A technology for phosphorus-sulfur compounds and compounds, applied in the field of chiral phosphorus-sulfur compounds and their Michael addition, can solve the problems of single activation mode and limited types of nucleophiles for phosphorus-sulfur compounds.

Pending Publication Date: 2021-02-26
SHENZHEN BAY LAB PINGSHAN TRANSLATIONAL MEDICINE CENT
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] The purpose of this application is to provide a chiral phosphorus-sulfur compound and its Michael addition method, aiming to solve the existing asymmetric phosphorus-Michael addition, based on the limited reaction of β,β-disubstituted Michael acceptors and the phosphorus The types of sulfur compounds as nucleophiles are limited and the activation mode is single

Method used

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  • Chiral phosphorus-sulfur compound and Michael addition method thereof
  • Chiral phosphorus-sulfur compound and Michael addition method thereof
  • Chiral phosphorus-sulfur compound and Michael addition method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0149] This example provides a (S)-diphenyl(1,1,1-trifluoro-3-nitro-2-phenylpropan-2-yl)phosphorus-sulfur compound and a preparation method thereof. The structural formula of the (S)-diphenyl (1,1,1-trifluoro-3-nitro-2-phenylpropan-2-yl) phosphorus sulfur compound is shown in the molecular structural formula I1 below:

[0150]

[0151] Its preparation steps are as follows:

[0152]In a 10ml test tube, the indenol-derived triazole carbene catalyst (0.01mmol, 0.1 equivalent (equiv.)) and the phosphorus-sulfur nucleophile (0.1mmol, 1.0equiv.), binaphthol (R- BINOL, 0.02mmol, 0.2equiv.) was dissolved in 1.6mL of a pretreated mixed solvent of ethylbenzene and cyclohexane with a ratio of 9:1, sealed with a rubber stopper, and then replaced with gas under an argon atmosphere (3 times) , slowly added lithium bis(trimethylsilyl)amide (LiHMDS) (1 mol / L, tetrahydrofuran / ethylbenzene solution, 8 μL, 0.08 equiv.), and replaced the gas again under an argon atmosphere (3 times). The tub...

Embodiment 2

[0155] This example provides a (S)-di-p-tolyl (1,1,1-trifluoro-3-nitro-2-phenylpropan-2-yl) phosphorus sulfur compound and a preparation method thereof. The structural formula of the (S)-di-p-tolyl (1,1,1-trifluoro-3-nitro-2-phenylpropan-2-yl) phosphorus sulfur compound is shown in molecular structural formula I2 below:

[0156]

[0157] Its preparation method refers to the preparation method of (S)-diphenyl (1,1,1-trifluoro-3-nitro-2-phenylpropan-2-yl) phosphorus sulfur compound in Example 1, the difference is that The p-tolylphosphosulfur compound (0.1 mmol) was used instead of the diphenylphosphosulfur compound. The reaction solution was directly separated and purified by silica gel column chromatography (ethyl acetate and n-hexane as eluents) to obtain the target product, a white solid, with a yield of 94% and an ee value of 95%.

[0158] The prepared product I2 is subjected to characterization data analysis, and the result is 1 H NMR (400MHz, CDCl 3 )δ7.91(dd, J=12....

Embodiment 3

[0160] This example provides a (S)-di-p-tolyl(1,1,1-trifluoro-2-(4-methoxyphenyl)-3-nitropropan-2-yl)phosphorus Compounds and methods for their preparation. (S)-two-p-tolyl (1,1,1-trifluoro-2-(4-methoxyphenyl)-3-nitropropane-2-yl)phosphorus sulfur compound has the following molecular structure formula I3 Shown:

[0161]

[0162] Its preparation method refers to the preparation method of (S)-diphenyl (1,1,1-trifluoro-3-nitro-2-phenylpropan-2-yl) phosphorus sulfur compound in Example 1, the difference is that Use p-tolyl phosphosulfur compound (0.1mmol) instead of diphenylphosphorsulfur compound, (E)-1-methoxy-4-(3,3,3-trifluoro-1-nitropropane-1 -en-2-yl)benzene was substituted for (E)-(3,3,3-trifluoro-1-nitroprop-1-en-2-yl)benzene (0.12 mmol). The reaction solution was directly separated and purified by silica gel column chromatography (ethyl acetate and n-hexane as eluents) to obtain the target product, a white solid, with a yield of 98% and an ee value of 93%.

[0163]...

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Abstract

The invention relates to the technical field of organic compound synthesis, and provides a chiral phosphorus-sulfur compound and a Michael addition method thereof. The Michael addition method of the chiral phosphorus-sulfur compound comprises the following steps: respectively providing a phosphorus-sulfur compound A and a nitroolefin compound B with the following structures: A: B: adding the phosphorus-sulfur compound A and the nitroolefin compound B into a reaction system containing an N-heterocyclic carbene catalyst, a proton additive, an alkali reagent and a water absorption additive; performing a reaction under the condition that the temperature is -80 - 25 DEG C to obtain the chiral beta-nitro phosphorus-sulfur compound shown as the following structural general formula (I), thereby completing the Michael addition of the chiral phosphorus-sulfur compound.

Description

technical field [0001] The application belongs to the technical field of organic compound synthesis, and in particular relates to a chiral phosphorus-sulfur compound and a Michael addition method thereof. Background technique [0002] Organophosphorus compounds are a class of very useful functional compounds, which have broad application prospects in the fields of organic synthetic chemistry, biochemistry, asymmetric catalysis, pesticides and pharmaceutical research. With the rapid development of asymmetric synthesis technology, organophosphate compounds with chiral centers have attracted considerable attention from chemists due to their potential biological activities, and their enantioselective synthesis has also achieved remarkable results. [0003] These chiral phosphate compounds can be used as synthetic intermediates to participate in asymmetric organocatalytic transformations, or as ligands to participate in metal-catalyzed asymmetric reactions. The asymmetric cataly...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/53C07F9/59C07F9/655C07F9/6553
CPCC07F9/5333C07F9/655345C07F9/5325C07F9/59C07F9/65515C07B2200/07
Inventor 黄湧陈杰安李恩
Owner SHENZHEN BAY LAB PINGSHAN TRANSLATIONAL MEDICINE CENT
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