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Method for asymmetrically synthesizing chiral beta-acetenyl ketone from beta-ketonic acid

An ethynyl ketone and a synthesis method technology, applied in chemical instruments and methods, preparation of organic compounds, preparation of carbon-based compounds, etc., can solve the problems of high preparation cost, harsh reaction conditions, low yield and the like, and achieve high reaction activity. , easy synthesis, good stereoselectivity

Inactive Publication Date: 2015-04-15
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

But this reaction needs to prepare β-ketoacid propargyl ester by the method for transesterification in advance, and reaction condition is harsh, and yield is low, and preparation cost is high

Method used

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  • Method for asymmetrically synthesizing chiral beta-acetenyl ketone from beta-ketonic acid
  • Method for asymmetrically synthesizing chiral beta-acetenyl ketone from beta-ketonic acid
  • Method for asymmetrically synthesizing chiral beta-acetenyl ketone from beta-ketonic acid

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] Example 1: Cu(CH 3 EN) 4 BF 4 Complexation with L-2-1 is used as a catalyst to catalyze the reaction to generate decarboxylated propargyl-substituted product II-1.

[0037] Add the metal precursor Cu(CH 3 EN) 4 BF 4 (0.015mmol, 5mol%) and chiral ligand L-2-1 (0.0165mmol, 5.5mol%), added 0.6ml of anhydrous methanol under nitrogen protection, and stirred at room temperature for 1 hour. Cool the reaction system to 0°C and add propargyl alcohol ester Ⅳ-1 (0.3mmol, 1equiv), β-keto acid Ⅲ-1 (0.3mmol, 1equiv) and N,N-diisopropylethylamine (0.36mmol , 1.2 equiv) was dissolved in 0.6 ml of anhydrous methanol, and then the solution was added to the above stirred catalyst solution under the protection of nitrogen, and the reaction was stirred at 0° C. for 12 h. After the reaction was completed, the reaction was quenched and extracted. Drying, rotary evaporation under reduced pressure, and column separation. White solid, 92% yield, 93%ee. 1 HNMR (400MHz, CDCl 3 ):δ2.29(s,...

Embodiment 2

[0039] Example 2: L-1-1 reacts as a ligand to generate product II-1

[0040] The ligand L-2-1 in Example 1 is replaced by the ligand L-1-1, Cu(CH 3 EN) 4 BF 4 With Cu(OAc) 2 ·H 2 O replaces, and temperature is room temperature, all the other are with embodiment 1. The reaction gave compound II-1 in 85% yield, 6% ee.

[0041]

Embodiment 3

[0042] Example 3: L-2-2 reacts as a ligand to generate product II-1

[0043] The ligand L-2-1 in Example 1 is replaced by the ligand L-2-2, Cu(CH 3 EN) 4 BF 4 With Cu(OAc) 2 ·H 2 O replaces, and temperature is room temperature, all the other are with embodiment 1. The reaction gave compound II-1 in 91% yield and 60% ee.

[0044]

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PUM

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Abstract

The invention relates to a method for synthesizing chiral beta-acetenyl ketone by catalytic intermolecular decarboxylation from beta-ketonic acid and a propargyl compound. A chiral copper catalyst adopted in the invention is synthesized in stiu from a copper salt and a chiral P,N,N-tridentate ligand in various polar solvents and nonpolar solvents. According to the invention, various chiral beta-acetenyl ketone compounds with substituent groups can be synthesized conveniently, and can obtain a percent enantiomeric excess as high as 95%. The method in the invention is advantaged by operational simplicity, available raw materials, wide substrate application range, high enantioselectivity, and the like.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a method for synthesizing chiral β-ethynyl ketones by intermolecular catalytic decarboxylation of β-keto acids and propargyl compounds. Background technique [0002] β-ethynyl ketone compounds are important raw materials for the synthesis of pyran, furan, pyrrole and many active natural products [(a) Lin, M.; Hao, L.; Ma, R.-D.; Zhan, Z.-P .Synthesis2010,2345.(b)Zhang,X.-M.;Tu,Y.-Q.;Jiang,Y.-J.;Zhang,Y.-Q.;Fan,C.-A.;Zhang, F.-M.Chem.Commun.2009, 4726.(c) Belting,V.;Krause,N.Org.Biomol.Chem.2009,7,1221.(d)Zhan,Z.-P.;Cai, X.-B.;Wang,S.-P.;Yu,J.-L.;Liu,H.-J.;Cui,Y.-Y.J.Org.Chem.2007,72,9838.(e)Nishibayashi , Y.; Yoshikawa, M.; Inada, Y.; Milton, M.D.; Hidai, M.; Uemura, S. Angew. Chem. Int. Ed. 2003, 42, 2681. (f) Wipf, P.; , L.T.; Rector, S.R.J.Org.Chem.1998, 63, 7132. (g) Arcadi, A.; Rossi, E. Tetrahedron1998, 54, 15253.]. The synthesis of this kind of compound is m...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C49/796C07C45/61B01J31/24C07C49/813C07C205/45C07C49/84C07C49/217C07C49/223C07D333/22C07D249/04C07C201/12
Inventor 胡向平朱付林
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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