Asymmetric synthesis method for 3,3'-diaryl substituted chiral spiro bisphenol compound

A technology of spirocyclic diphenols and compounds, which is applied in the field of asymmetric synthesis of chiral spirocyclic diphenolic compounds, can solve problems such as limitations of spirocyclic partial modification, achieve high industrial production value, high yield, and enantioselective good sex effect

Active Publication Date: 2019-03-01
CHINA PHARM UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The asymmetric catalytic synthesis methods reported so far can realize abundant structural modification of the benzene ring part of SPINAL, but the modification of the spiro ring part is relatively limited, and there are still no reports in the literature on chiral rings substituted with aryl groups at the 3 and 3′ positions. Asymmetric Synthesis of Sexual Spiral Diphenols (Formula C)

Method used

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  • Asymmetric synthesis method for 3,3'-diaryl substituted chiral spiro bisphenol compound
  • Asymmetric synthesis method for 3,3'-diaryl substituted chiral spiro bisphenol compound
  • Asymmetric synthesis method for 3,3'-diaryl substituted chiral spiro bisphenol compound

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Embodiment 1

[0049] Using the following reaction scheme, taking the preparation of compound I-a as an example, the general preparation method of I described in the present invention is described in detail in this embodiment:

[0050]

[0051] Compound 1 (0.5g, 3.6mmol) and acetone (132μL, 1.8mmol) were added into the reaction flask, 40% NaOH aqueous solution (0.5mL) was slowly added dropwise at 0°C, moved to room temperature, and reacted for 8h. Pour the reaction solution into an ice-water bath, slowly add 2M HCl (4mL) dropwise, adjust the pH to 4-5, a solid precipitates, continue to stir for 0.5h, filter with suction, wash the filter cake with a large amount of water to obtain a crude product, which is recrystallized to obtain a yellow Solid 0.64g, yield 83%. Spectral data:

[0052] ESI-MS (m / z): 422.9; 1 H NMR (500MHz, Acetone) δ8.83(s, 2H), 8.05(d, J=15.9Hz, 2H), 7.55(d, J=8.7Hz, 2H), 7.41(d, J=2.8Hz, 2H ), 7.23 (d, J=15.9Hz, 2H), 6.94 (dd, J=8.7, 2.8Hz, 2H).

Embodiment 2

[0054] Compound 1 (0.5g, 3.6mmol) and acetone (132μL, 1.8mmol) were added into the reaction flask, 40% KOH aqueous solution (0.5mL) was slowly added dropwise at 0°C, moved to room temperature, and reacted for 8h. Pour the reaction solution into an ice-water bath, slowly add 2M HCl dropwise, adjust the pH to 4-5, a solid precipitates, continue to stir for 0.5h, filter with suction, wash the filter cake with a large amount of water to obtain a crude product, and obtain a yellow solid 0.58g after recrystallization , yield 75%.

Embodiment 3

[0056] Compound 1 (1.0 g, 7.2 mmol) and acetone (264 μL, 3.6 mmol) were added into the reaction flask, 40% NaOH aqueous solution (1.6 mL) was slowly added dropwise at 0° C., moved to room temperature, and reacted for 8 h. Pour the reaction solution into an ice-water bath, slowly add 2M HCl dropwise, adjust the pH to 4-5, a solid precipitates, continue to stir for 0.5h, filter with suction, wash the filter cake with a large amount of water to obtain the crude product, and obtain 1.0 g of a yellow solid after recrystallization , yield 67%.

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Abstract

The invention discloses an asymmetric synthesis method for a 3,3'-diaryl substituted chiral spiro bisphenol compound. The method comprises the steps that acetone serves as a raw material and is subjected to condensation reaction with substituted benzaldehyde so as to obtain I; under the action of a chiral rhodium catalyst, the compound I and an aryl boron reagent are subjected to enantioselectivesynthesis so as to obtain II; and under the catalysis of Bronsted acid or Lewis acid, the compound II is subjected to intramolecular Friedel-Crafts reaction so as to prepare a compound III. The synthesis method has the advantages that chiral raw materials are not needed, splitting is not needed, the yield is high, the enantioselectivity is good and the like; in an amplified synthesis process, theamount of the chiral rhodium catalyst can be as low as 0.5 mol%, and industrial production application values are achieved.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and specifically relates to an asymmetric synthesis method of 3,3'-diaryl substituted chiral spirocyclic diphenol compounds. Background technique [0002] 1,1′-spiroindane-7,7′-diol (SPINOL) compounds with axial chirality occupy an important position in the field of asymmetric catalysis. Based on the SPINOL framework, a large number of chiral catalyst ligands have been developed. These chiral ligands have shown excellent chirality in asymmetric hydrogenation reactions, asymmetric carbon-carbon bond and carbon-heterobond catalytic reactions. The sex-inducing energy has been improved, and it has achieved great success, which fully reflects the structural advantages of this type of skeleton. The report about the chiral synthetic method of SPINOL can be divided into two big classes at present, the first kind is by the strategy synthesis (Tetrahedron-Asymmetry 1999,10,125; Tetrahedron:-Asym...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C37/00C07C39/42C07C41/18C07C43/23C07C67/317C07C69/94B01J31/22C07C45/69C07C49/784
CPCB01J31/189B01J2231/32B01J2531/0213B01J2531/16C07B2200/07C07C39/42C07C43/23C07C45/69C07C45/74C07C69/94C07C2603/94C07C49/784C07C49/245C07C49/248C07C49/255
Inventor 窦晓巍殷龙邢峻豪
Owner CHINA PHARM UNIV
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