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Monophosphine ligand based on tetramethyl spirobiindane skeleton, as well as intermediate, preparation method and application thereof

A technology of tetramethylspirodihydroindene and skeleton, applied in chemical instruments and methods, preparation of organic compounds, preparation of oximes, etc., can solve problems such as inability to obtain

Active Publication Date: 2018-10-16
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, it is obvious that the corresponding 3,3,3',3'-tetramethyl-1,1'-spiroindane-7,7'-diol and its derivative

Method used

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  • Monophosphine ligand based on tetramethyl spirobiindane skeleton, as well as intermediate, preparation method and application thereof
  • Monophosphine ligand based on tetramethyl spirobiindane skeleton, as well as intermediate, preparation method and application thereof
  • Monophosphine ligand based on tetramethyl spirobiindane skeleton, as well as intermediate, preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0068]

[0069] Add 2g (6mmol) III-a racemic compound in the there-necked flask, add 150mL dichloromethane under nitrogen protection, cool in an ice bath, add 0.9mL trifluoroacetic acid (12mmol), add 4.28g m-chloroperoxybenzene in three times 27mmol of formic acid (m-CPBA) was stirred and dissolved, and the reaction solution was colorless and transparent. After stirring overnight at room temperature for 16 hours, the reaction solution turned light yellow. TLC plate monitoring reaction (with 2,4-dinitrophenylhydrazine color development), reaction finishes; Add 50 milliliters of sodium sulfite saturated solutions to quench the reaction, water successively, saturated sodium bicarbonate and saturated sodium chloride solution wash the organic phase, no Dry over sodium sulfate, concentrate to dryness under reduced pressure, add 10mL methanol to dissolve the residual solid, slowly add 20mL 3mol / L sodium hydroxide solution with stirring, react overnight at room temperature, monitor...

Embodiment 2

[0072]

[0073]Add 1.44g (R)-III-b compound (4mmol) in the there-necked flask, add 150mL dichloromethane under nitrogen protection, ice bath cooling, add 3.2g m-chloroperoxybenzoic acid (m-CPBA) 16mmol in three times, Add 0.6mL trifluoroacetic acid (8mmol), stir to dissolve, and the reaction solution is colorless and transparent. After stirring overnight at room temperature for 15 hours, the reaction solution turned light yellow. TLC plate monitoring reaction (with 2,4-dinitrophenylhydrazine color development), reaction finishes; Add 30 milliliters of sodium sulfite saturated solutions to quench the reaction, water successively, saturated sodium bicarbonate and saturated sodium chloride solution wash the organic phase, no Dry over sodium sulfate, concentrate to dryness under reduced pressure, add 40mL methanol to dissolve the residual solid, slowly add 16mL 1mol / L sodium hydroxide solution with stirring, react overnight at room temperature for 12 hours, monitor the reaction...

Embodiment 3

[0076]

[0077] According to the experimental procedure of Example 2, compound (R)-IIII-b was replaced with (R)-III-d to obtain product (R)-II-d (yield 92%). 1 H NMR (400MHz, CDCl 3 )δ6.55(s,2H),5.09(s,2H),3.71(s,6H),2.47(d,J=13.0Hz,2H),2.29(s,6H),2.22(d,J=13.0 Hz,2H),1.37(s,6H),1.31(s,6H).

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Abstract

The invention discloses monophosphine ligand based on a tetramethyl spirobiindane skeleton, as well as an intermediate, a preparation method and application thereof. The monophosphine ligand adopts acompound with a structure as shown in a general formula I or I' or an enantiomer, a racemate or a diastereoisomer of the compound, and comprises phosphorous ester ligand, phosphorous ester ligand, phosphoramidite ester ligand, phosphoric acid and phosphamide. The monophosphine ligand takes a known 3, 3, 3', 3'-tetramethyl-1, 1'-spirobiindane-7, 7'-dimethyl aldehyde as a raw material, and is formedthrough a formula II which is taken as a preparation route of a key intermediate. The novel monophosphine ligand can serve as ligand to be used for organic reaction of metal catalysis or be directlyused for catalyzing the organic reaction, can particularly serve as chiral monophosphine ligand to be widely applied to multichiral catalytic reaction including asymmetric addition, asymmetric hydrogenation, asymmetric coupling and asymmetric allylic alkylation, and has economical practicability and an industrial application prospect.

Description

technical field [0001] The invention relates to the technical field of organic chemistry, and relates to a novel monophosphine ligand based on a tetramethylspiroindane skeleton, an intermediate thereof, a preparation method and application thereof. Such monophosphine ligands can be used in metal-catalyzed coupling reactions or asymmetric reactions, or directly catalyze organic reactions. Background technique [0002] Asymmetric catalysis is one of the most active research fields in synthetic chemistry today, and this technology obtains chiral molecules in the most direct and effective way. It has the advantages of chiral multiplication, high enantioselectivity, economy and easy industrialization. Realizing highly efficient and highly selective asymmetric catalytic reactions is a challenging subject in the field of synthetic chemistry, and the key scientific problem is to develop and discover new and efficient chiral ligands and their catalysts. At present, the design and s...

Claims

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Application Information

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IPC IPC(8): C07F9/6574C07F9/6571C07F15/00C07C37/56C07C39/17C07C39/42C07C41/26C07C43/23B01J31/22C07B53/00C07D209/44C07C303/40C07C311/16C07D291/08C07C231/12C07C233/47C07D215/40C07C249/12C07C251/44
CPCC07B53/00C07C37/56C07C39/17C07C39/42C07C41/26C07C43/23C07C231/12C07C233/47C07C249/12C07C251/44C07C303/40C07C311/16C07D209/44C07D215/40C07D291/08C07F9/657154C07F9/65744C07F15/006C07F15/0066C07F15/0073C07F15/008B01J31/1805B01J31/185B01J31/186C07C2601/16C07C2603/94C07B2200/07B01J31/2291B01J2531/824B01J31/1845B01J2531/822B01J2231/344B01J2231/46B01J2231/645B01J31/1865B01J31/189
Inventor 林旭锋单环宇周巧霞
Owner ZHEJIANG UNIV
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