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Planar chiral ferrocene compound, synthetic method and application

A technology of chiral ferrocene and synthesis method, which is applied in the field of planar chiral ferrocene compounds, can solve the problems of lack of efficient synthesis methods, achieve excellent yield and enantioselectivity, mild reaction conditions, and simple operation Effect

Active Publication Date: 2016-01-20
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] In view of the wide use of planar chiral ferrocenes, but the lack of efficient synthetic methods

Method used

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  • Planar chiral ferrocene compound, synthetic method and application
  • Planar chiral ferrocene compound, synthetic method and application
  • Planar chiral ferrocene compound, synthetic method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] Example 1: Partial amino acid screening results

[0039]

[0040] In the reaction formula, Pd(OAc) 2 Represents palladium acetate, ligand represents the chiral amino acid ligand, mol describes the mole, K 2 CO 3 Represents potassium carbonate, equiv. represents equivalent, DMA represents N,N-dimethylacetamide, air represents air, and T represents temperature.

[0041] Add the corresponding benzofuran 2a and DMA (1.5mL) to the dry Schlenk reaction flask, followed by amino acid (0.06mmol), palladium acetate (0.03mmol), potassium carbonate (0.45mmol), benzoquinone (0.03mmol) , water (1.2 mmol) and ferrocene 1a (0.3 mmol). The reaction was heated under air atmosphere. After the reaction was completed, the reaction was quenched with saturated sodium bicarbonate and extracted with ethyl acetate. The organic phases were combined, washed successively with water and saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent residue was removed under ...

Embodiment 2

[0045] Embodiment 2: the asymmetric synthesis of planar chiral ferrocene compound (Rp)-P or (Sp)-P

[0046] Reaction 1

[0047]

[0048] Reaction 2

[0049]

[0050] In reaction formula 1, Pd(OAc) 2 Represents palladium acetate, Boc-L-Ile-OH represents (S)-N-tert-butoxycarbonyl isoleucine, mol describes mole, equiv. describes equivalent, K 2 CO 3 stands for potassium carbonate, BQ stands for p-quinone, H 2 O represents water, DMA represents N,N-dimethylacetamide, and air represents air; in Reaction Formula 2, Boc-D-Ile-OH represents (R)-N-tert-butoxycarbonylisoleucine.

[0051] Add palladium acetate (6.7mg, 0.03mmol), Boc-L-Ile-OH (13.9mg, 0.06mmol) or Boc-D-Ile-OH (13.9mg, 0.06mmol), potassium carbonate to a dry Schlenk reaction flask (62.2mg, 0.45mmol), BQ (3.2mg, 0.03mmol), water (21.6mg, 1.2mmol) and DMA (1.5mL). The corresponding ferrocene substrate 1 (0.3 mmol) and heteroarene 2 (0.6 mmol) were added. Heated to 80°C under air atmosphere to react. After the ...

Embodiment 3

[0132] Embodiment 3: the synthesis of (Rp)-II or (Sp)-II

[0133] Reaction 1

[0134]

[0135] Reaction 2

[0136]

[0137] t-BuLi means tert-butyl lithium, EX means benzophenone or diphenylphosphine chloride or trimethylchlorosilane or diphenyl disulfide, Et 2 O represents ether.

[0138] Under argon protection, add (R p )-S-1 or (S p )-S-1(1equiv.) and dry diethyl ether (0.06mol / L), cooled to -78°C, added t BuLi (1.5 equiv.). The reaction was stirred at -78°C for 5 hours. Then, a diethyl ether solution (2.0 equiv. 0.2 mol / L) of the electrophile was added dropwise to the reaction system. The reaction was returned to room temperature, stirred overnight, and reacted for 2-20 hours. The reaction mixture was quenched by adding ice water and extracted with ethyl acetate. The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and filtered. The solvent was removed under reduced pressure and purified by column chromatography (ethylaceta...

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Abstract

The invention relates to a planar chiral ferrocene compound, a synthetic method and application. The planar chiral ferrocene compound has the structural formula shown as follows. Amine methyl substitutional ferrocene and heterocyclic aromatics are used as raw materials, chiral amino acid and palladium are used as catalysts, and the planar chiral ferrocene compound is synthesized with high efficiency and high enantioselectivity through double carbon-hydrogen bond activation. The planar chiral ferrocene compound can be conveniently converted into chiral ligand to be applied in a metal catalysis asymmetric reaction.

Description

technical field [0001] The invention relates to a planar chiral ferrocene compound, a synthesis method and an application. The method can take aminomethyl substituted ferrocene, substituted heterocyclic aromatic hydrocarbons as raw materials, chiral amino acid and palladium as catalyst, and synthesize this class with high efficiency and high selectivity (high enantioselectivity, high regioselectivity). Planar chiral ferrocenes. This kind of planar chiral ferrocene compound can be easily converted into chiral ligands, and can be applied in some metal-catalyzed asymmetric reactions. Background technique [0002] Chiral biaryls are very common frameworks in the fields of medicinal chemistry, asymmetric catalysis, and materials chemistry (Bringmann, G.; Gulder, T.; Gulder, T.A.M.; Breuning, M. Chem. Rev. 2011, 111, 563– 639. Brunel, J.M.; Chem. Rev. 2005, 105, 857–897. Murphy, A.R.; Fréchet, J.M.J. Chem. Rev. 2007, 107, 1066–1096.). The most commonly used method of building t...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F17/02B01J31/22C07C69/618C07C67/343C07C33/20C07C33/18C07C29/40
Inventor 游书力高得伟顾庆
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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