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Method for organically catalyzing asymmetric conjugated addition of ketene and organic phosphorus compound

An organocatalytic enone and conjugate addition technology, applied in organic chemistry methods, asymmetric synthesis, organic compound/hydride/coordination complex catalysts, etc., can solve problems such as space congestion, poor selectivity, and difficult problems. Achieve high catalytic efficiency, less catalyst consumption and good selectivity

Inactive Publication Date: 2011-09-21
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the conjugate addition reaction between similar asymmetric organophosphine compounds and enones is still a major problem in organic synthesis.
This may be inherently difficult on the one hand due to steric crowding of intermediates formed by chiral secondary amines and ketones
On the other hand, there are 1,2-addition and 1,4-addition in the reaction of organic phosphine compound and enone, and the selectivity is poor

Method used

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  • Method for organically catalyzing asymmetric conjugated addition of ketene and organic phosphorus compound
  • Method for organically catalyzing asymmetric conjugated addition of ketene and organic phosphorus compound
  • Method for organically catalyzing asymmetric conjugated addition of ketene and organic phosphorus compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] In 2 mL of dichloromethane, add cyclohexenone (0.288 g, 3.0 mmol), diphenoxyphosphine (0.202 g, 1 mmol), 1,2-diaminocyclohexane (R, R) and quinine to construct Primary thiourea catalyst (R 2 is quinine, X is sulfur, cyclohexanediamine is R, R configuration) (0.048g, 0.1mmol), after the addition of the material, the reaction conversion is complete after stirring at 20°C to 25°C for 48h. The reaction solution was concentrated under reduced pressure and separated by silica gel column chromatography (petroleum ether / ethyl acetate=3:1) to obtain 0.280 g of a white solid with a yield of 94% and ee=90%. 1 HNMR (400MHz, CDCl 3 ): δ (ppm) 7.78-7.73 (m, 4H), 7.52-7.50 (m, 6H), 2.81-2.62 (m, 2H), 2.39-2.34 (m, 2H), 2.30-2.28 (m, 1H) , 2.21-2.17(m, 1H), 1.96-1.83(m, 2H), 1.72-1.69(m, 1H). 13 CNMR (100MHz, CDCl 3): δ (ppm) 209.8, 209.6; 131.9; 131.9; 130.9; 130.8; 128.9; 128.8; 41.2; 39.3; 38.1; 26.4; 23.3. HRMS (ESI): Theoretical M + (C 18 h 19 o 2 P+H) was m / z 299.1201, a...

Embodiment 2

[0040] The difference from Example 1 is that cyclohexenone (0.0288g, 0.3mmol), diphenoxyphosphine (0.020g, 0.1mmol), 1,2-diaminocyclohexane (R, R) and quinine The constructed primary thiourea catalyst (R 2 is quinine, X is sulfur, cyclohexanediamine is R, R configuration) (0.0048g, 0.01mmol), the yield is 93%, ee=90%.

[0041] Implementation example 2

[0042] The difference from Example 1 is that cyclohexenone (0.0288g, 0.3mmol), diphenoxyphosphine (0.020g, 0.1mmol), 1,2-diaminocyclohexane (R, R) and quinine The constructed primary thiourea catalyst (R 2 is quinine, X is sulfur, cyclohexanediamine is R, R configuration) (0.0048g, 0.01mmol), the yield is 93%, ee=90%.

Embodiment 3

[0044] The difference from Example 1 is that cyclohexenone (0.192g, 2.0mmol), diphenoxyphosphine (0.202g, 1mmol), 1,-diaminocyclohexane (R, R) and quinine are added to construct The primary thiourea catalyst (R 2 is quinine, X is sulfur, cyclohexanediamine is R, R configuration) (0.048g, 0.1mmol), the yield is 93%, ee=90%.

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Abstract

The invention relates to a chemical reaction process of asymmetric conjugated addition, in particular to a method for organically catalyzing asymmetric conjugated addition of ketene and an organic phosphorus compound. In the method, the ketene and the organic phosphorus compound serving as raw materials are reacted in a solvent at the temperature of between -40 and 40DEG C for 2 to15 days to form a conjugated addition reactant, wherein multifunctional catalysts respectively containing one or more than one primary amine, one or more than one tertiary amine and one ore more than one urea or thiourea functional group are taken as a catalyst system. The method has the characteristics that: the catalyst using amount is small, the catalytic efficiency is high, the yield and optical selectivity are high, conditions are mild, the method is easy and convenient to implement and the like.

Description

technical field [0001] The invention relates to a chemical reaction process of asymmetric catalytic conjugated addition, specifically a new method for organically catalyzed conjugated addition of enone and organic phosphine compound. Background technique [0002] Chiral phosphine compounds are important ligands for asymmetric metal catalysis and can also be used as catalysts in organocatalytic reactions. The asymmetric conjugate addition of organophosphine to alkenes is a very useful process for the construction of C-P bonds and the synthesis of chiral phosphine compounds. Alkyl phosphine hydrogen compounds, phosphine oxides, phosphonates and phosphonites all have good nucleophilic properties, and are easy to interact with Michael acceptors such as α, β-enal, nitro Conjugate addition of alkenes and imines etc. Due to the construction of the C-P bond, many phosphine ligands as well as natural products and analogs can be synthesized. [0003] In the past few years, with the...

Claims

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Application Information

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IPC IPC(8): C07B53/00C07F9/53B01J31/02
Inventor 叶金星梁鑫淼文石钢
Owner EAST CHINA UNIV OF SCI & TECH
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