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A kind of chiral (e)-2-(1,3-diarylallyl) dimethyl malonate compound and preparation method thereof

A technology of aryl allyl acetate and dimethyl malonate, which is applied in the field of organic synthesis and achieves the effects of high stereoselectivity, good reactivity and wide application range of substrates

Active Publication Date: 2022-07-15
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[(a) Xiao L, Mereiter K, Spindler F, et al. A straightforward and modular synthesis of enantiopure C 2 -and C 1 -symmetrical 2,2″-phosphino-1,1″-biferrocenes[J].Tetrahedron Asymmetry,2001,12(8),1105-1108.(b)Synthesis of Chiral C 2 -Symmetric Bisferrocenyldiamines.X-ray Crystal Structure of Ru(2)Cl 2 2CHCl 3 (2=N1,N2-Bis{(R)-1-[(S)-2-(diphenylphosphino)]ferrocenylethyl}-N1,N2-dimethyl-1,2-ethanediamine)[J].Inorganic chemistry,1999, 38(5),893-896.] However, there are few reports on the use of the P, N ligands in this paper for allyl substitution reactions

Method used

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  • A kind of chiral (e)-2-(1,3-diarylallyl) dimethyl malonate compound and preparation method thereof
  • A kind of chiral (e)-2-(1,3-diarylallyl) dimethyl malonate compound and preparation method thereof
  • A kind of chiral (e)-2-(1,3-diarylallyl) dimethyl malonate compound and preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0041] Embodiment 1: (n-allyl) PdCl 2 The complexation with L-1-1 is used as a catalyst to catalyze the reaction to generate (E)-2-(1,3-diphenylallyl) dimethyl malonate substituted product III-1.

[0042] Add metal precursor (η-allyl)PdCl to the reaction flask 2 (0.005 mmol, 5 mol %) and chiral ligand L-1-1 (0.011 mmol, 5.5 mol %), 1.0 mL of anhydrous toluene was added under nitrogen protection, and the mixture was stirred at room temperature for 1 hour. Then (E)-1,3-diphenylallyl acetate I-1 (0.5 mmol, 1.0 equiv), dimethyl malonate compound II-1 (1.0 mmol, 3 equiv) and KOAc ( 0.36 mmol, 1.2 equiv) was dissolved in 2.0 mL of anhydrous toluene, then the solution was added to the above stirred catalyst solution under nitrogen protection, and the reaction was stirred at 25° C. for 12 h. After the reaction was completed, it was concentrated under reduced pressure until almost solvent-free, separated by silica gel column chromatography, concentrated under reduced pressure, and dr...

Embodiment 2

[0046] Example 2: L-1-2 reacts as a ligand to generate product III-1

[0047] The ligand L-1-1 in Example 1 was replaced with the ligand L-1-2, and the rest was the same as that in Example 1, and the reaction was carried out to obtain compound III-1, 65% yield, 8.9% ee.

[0048] The structural formula of L-1-2 is as follows:

[0049]

Embodiment 3

[0050] Example 3: L-1-3 reacts as a ligand to generate product III-1

[0051] The ligand L-1-1 in Example 1 was replaced with the ligand L-1-3, and the rest was the same as that in Example 1, and the reaction was carried out to obtain compound III-1, 77% yield, 82% ee.

[0052] The structural formula of L-1-3 is as follows:

[0053]

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Abstract

The invention provides a chiral (E)-2-(1,3-diarylallyl) dimethyl malonate compound and a preparation method thereof. The method adopts a chiral Pd catalyst to catalyze (E)- Asymmetric substitution reaction of 1,3-diarylallyl acetate compounds with dimethyl malonate, high enantioselectivity to prepare a series of chiral (E)-2-(1,3-diaryl A method for dimethyl allyl)malonate compound. The reaction starts with (n-allyl)PdCl 2 Metal complexes generated in situ with chiral P,N-ligands are used as catalysts, and are carried out in various polar and non-polar solvents at room temperature. The present invention has the characteristics of relatively mild reaction conditions, readily available raw materials, high stereoselectivity, wide substrate adaptation range and the like.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a palladium-catalyzed asymmetric substitution reaction between (E)-1,3-diarylallyl acetate compounds and dimethyl malonate compounds, high enantioselectivity Methods for the preparation of a series of chiral (E)-2-(1,3-diarylallyl)malonate dimethyl esters. Background technique [0002] Since Trost et al. reported the first example of Pd-catalyzed asymmetric allyl substitution reaction in 1977, after more than 20 years of development, great progress has been made in catalyzing asymmetric allyl substitution reactions. It was designed and synthesized and showed good chirality-inducing activity. These ligands include phosphine ligands such as monophosphine, bisphosphine, bis-nitrogen, phosphine-nitrogen, and many other chiral ligands with double redundant atoms. [(a) X.-P.Hu, H.-C.Dai, X.-Q.Hu, H.-L.Chen, J.-W.Wang, C.-M.Bai, Z.Zheng, Ferrocenylphosphine-imine ligands ...

Claims

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Application Information

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IPC IPC(8): C07C67/343C07C69/65B01J31/24
CPCC07C67/343B01J31/2404B01J2531/824B01J2231/4205C07C69/65
Inventor 胡向平危得全
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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