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Asymmetric copper compound and cyclopropanation reaction with it

A copper complex and asymmetric technology, applied in the field of asymmetric copper complexes and cyclopropane compounds, can solve the problems of poor stability, difficult handling, complex copper complexes, etc., and achieve the effect of low price

Inactive Publication Date: 2002-12-11
SUMITOMO CHEM CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] However, these methods are not always satisfactory as industrial production methods because complex steps are required to prepare copper complexes and their handling is not easy due to poor stability

Method used

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  • Asymmetric copper compound and cyclopropanation reaction with it

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Experimental program
Comparison scheme
Effect test

Embodiment 1A

[0199] After replacing the atmosphere in a glass Schlenk tube with an inner volume of 50 ml with nitrogen, 9.8 mg (0.022 mmol) of 2,2'-isopropylidenebis{(4R)-4-phenyl-5 was added at room temperature, 5-diethyl-2-oxazoline}, 4mg (0.02mmol) of copper acetate monohydrate and 5ml of ethyl acetate, after stirring the mixture for 0.5 hours, added 3.0mg (0.02mmol) of trifluoromethanesulfonic acid , and the mixture was stirred at room temperature for 1 hour to prepare a complex catalyst solution.

Embodiment 1B

[0201] 11 g (100 mmol) of 2,5-dimethyl-2,4-hexadiene was added to the complex catalyst prepared in Example 1A. Then 10 ml of a solution of ethyl diazoacetate in toluene (containing 10 mmol of ethyl diazoacetate) was added thereto within 2 hours, during which the reaction temperature was kept at 20°C. The mixture was then kept at 20° C. for 30 minutes. The yield and ratio of trans / cis isomers of ethyl chrysanthemum acid as the product were analyzed by GC, and the optical purity was analyzed by LC. The yield of ethyl chrysanthemic acid was 88.4% (relative to the ethyl diazoacetate added), trans / cis = 74 / 26, the optical purity was 84% ​​e.e. (trans) and 24% e.e. (cis ).

Embodiment 1C

[0203] The same reaction as in Example 1B was carried out, except that tert-butyl diazoacetate was used instead of ethyl diazoacetate in Example 1B. After the product was converted to the 1-menthyl derivative, its optical purity was analyzed by GC.

[0204] The yield of tert-butyl chrysanthemic acid was 81.5% (relative to the added tert-butyl diazoacetate), trans / cis = 83 / 17, optical purity was 94% e.e. (trans) and 60% e.e. ( cis).

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Abstract

There are disclosed asymmetric copper complex comprising, as components, (a) an optically active bisoxazoline compound of formula (1): <CHEM> wherein R<1> and R<2> are different and each represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a phenyl or aralkyl group which may be substituted, R<3> and R<4> each represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a phenyl or aralkyl group which may be substituted, or R<3> and R<4> may be bonded to each other to form a C3-5 cyclic alkylene group, R<5> represents a hydrogen atom or a C1-6 alkyl group, or the two R<5> groups may be bonded to each other to represent a C3-5 cyclic alkylene group, (b) a monovalent or divalent copper compound, and (c) a strong acid or a Lewis acid or a mixture thereof, and a process for producing an optically active cyclopropanecarboxylate using the same.

Description

technical field [0001] The present invention relates to an asymmetric copper complex containing as a component an optically active A bisoxazoline compound, a copper compound, and strong or Lewis acids or mixtures thereof. Background technique [0002] Optically active cyclopropane carboxylate is an important compound as an intermediate for the preparation of pharmaceuticals and agricultural chemicals. For example, (+)-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic acid, known as chrysanthemum-monocarboxylic acid, constitutes the acid group of synthetic pyrethroid-type insecticides point. (+)-2,2-Dimethylcyclopropanecarboxylic acid is known to be useful as an intermediate in the synthesis of β-lactam type antibiotics. [0003] The generally known method of preparing optically active cyclopropanecarboxylic acid derivatives directly by synthesis is to use optically active bis[2-(4,5-diphenyl-1,3-oxane in the presence of an asymmetric copper complex. Azolinyl)]me...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F1/08B01J27/06B01J31/02B01J31/18C07C67/347C07F1/00
CPCB01J27/06B01J31/0231B01J31/182B01J2231/325B01J2531/16C07B2200/07C07C67/347C07F1/005C07C69/74C07C69/747C07F1/08
Inventor 山本三千男铃鸭刚夫板垣诚
Owner SUMITOMO CHEM CO LTD
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