A process for the preparation of optically active cyclohexenones

一种旋光性、非强制的技术，应用在有机化学方法、碳基化合物制备、化学仪器和方法等方向

Active Publication Date: 2007-02-21
FIRMENICH SA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0010] In order to solve the above-mentioned problems, the present invention relates to a method aimed at synthesizing optically active cyclohexenone derivatives by intramolecular aldol condensation in a single step.

Method used

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  • A process for the preparation of optically active cyclohexenones
  • A process for the preparation of optically active cyclohexenones
  • A process for the preparation of optically active cyclohexenones

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Embodiment approach

[0081] According to another embodiment of the present invention, the preferred additives are NaH, KH, 4 Ȧ type anhydrous zeolite, t BuONa or anhydrous KOH, NaOH, NaCl, Na 2 CO 3 、Na 2 SO 4 .

[0082] Said additives can be added to the reaction medium in a wide range of amounts, depending on the exact nature of the additive. Nevertheless, additions of more than three times the theoretical amount required to capture all the water theoretically produced do not provide any appreciable additional benefit.

[0083] The process of the present invention can be carried out in the presence or absence of a solvent, but in any case the reaction advantageously takes place under anhydrous conditions such as less than 0-5% w / w water. Those skilled in the art will appreciate that the presence of a solvent is only necessary if the starting diketone (I) is a solid compound under the reaction conditions.

[0084] However, according to a preferred embodiment of the invention, independent of...

Embodiment 1

[0089] Preparation of Optically Active 14-Methyl-bicyclo[9.4.0]pentadeca-1(11)-en-12-one

[0090]

[0091] a) General procedure:

[0092] Under an inert environment, add 126 mg 3-methyl-1,5-cyclopentadecanedione, 3 ml dry THF, optional 200 mg anhydrous 4 Å molecular sieves or 2 molar equivalents of NaH, and dissolve in Na alkoxides or K alkoxides 1-12 shown in Table 1 were dried in THF. The total amount of THF present was calculated to keep the starting diketone concentration between 0.1-0.4 mol / L at the beginning of the reaction.

[0093] The reaction mixture was stirred at room temperature, followed by GC analysis. To quench the reaction, the mixture was hydrolyzed with water or 2N aqueous HCl. After extracting the aqueous layer with diethyl ether, the organic layer was washed with MgSO 4 Dry and filter. The solvent was removed under vacuum and the residue was purified by flash chromatography or by bulb to bulb distillation to give the desired product, i.e. (S)-14-me...

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Abstract

The present invention relates to a process for the preparation of an optically active 5-substituted cyclohexenone (II) by treating an achiral macrocyclic 3-substituted-1,5-diketone (I) in the presence of an optically active sodium, potassium or cesium alkoxide.

Description

technical field [0001] The present invention relates to the field of organic synthesis, more specifically, relates to a method for preparing optically active 5-substituted cyclohexenone, which method is according to the following scheme 1, through the presence of optically active sodium, potassium or cesium alkoxide The following treatment of achiral macrocyclic 3-substituted-1,5-diones is achieved: [0002] Scheme 1: the inventive method [0003] Background technique [0004] Optically active cyclohexenone derivatives are useful intermediates or building blocks for the synthesis of a wide variety of more complex compounds such as steroids or macrocyclic ketones. [0005] Although this is true, to the best of our knowledge the prior art has only reported a method for the cyclization of achiral diketones to optically active cyclohexenone derivatives in the presence of a chiral cocatalyst (see C. Agami et al. in Bulletin de la Société Chimique de France, 1987, 358). [0...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/66C07C49/623
CPCC07B2200/07C07C45/66C07C49/623
Inventor 奥利弗·克诺普夫
Owner FIRMENICH SA
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