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Silicon-center chiral silicon-oxygen compound and preparation method thereof

A technology of silicon oxide compounds and compounds, applied in the direction of silicon organic compounds, chemical instruments and methods, compounds of group 4/14 elements of the periodic table, etc., can solve the limitation of chiral silicon compound design and application, and cannot obtain satisfactory ee value , limited range of substrates, etc., to achieve the effects of wide application range of substrates, excellent glum value, and atom economy

Active Publication Date: 2021-07-23
SOUTH UNIVERSITY OF SCIENCE AND TECHNOLOGY OF CHINA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although there are many methods for synthesizing siloxanes and silyl ethers, methods for obtaining chiral center compounds are rarely reported, which limits the design and application of chiral silicon compounds.
[0003] At present, silicon chiral silyl ethers can be obtained by optical resolution and dynamic resolution of chiral alcohol auxiliary agents, but the scope of substrates is limited, the efficiency is low and the atom economy is poor, and some other methods cannot obtain satisfactory ee values.

Method used

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  • Silicon-center chiral silicon-oxygen compound and preparation method thereof
  • Silicon-center chiral silicon-oxygen compound and preparation method thereof
  • Silicon-center chiral silicon-oxygen compound and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0087] Synthesis of Dihydrosilane Substrates

[0088]

[0089] Method A: Add tBuLi (1.3M pentane solution, 1.1 equiv) dropwise to aryl bromide (1.0 equiv) in THF (0.5M) at -78°C under the protection of argon, and stir at -78°C 1 h, then add tBuSiCl in 10 mL THF 3 (1.2 equivalents). The mixture was stirred for an additional 1 h at -78 °C, then allowed to warm to room temperature and stirred overnight. The reaction was cooled again to -78 °C and LiAlH was added dropwise 4 (2.5M in THF, 2.0 eq.) and stirred at -78°C for a further 30 min, then the mixture was allowed to warm to room temperature and stirred for 8 h. Finally, the reaction mixture was heated at -78 °C with saturated NH 4 Cl was quenched, and after warming to room temperature, the mixture was filtered and washed with Et 2 Washed with O, the organic layers were combined and washed with MgSO 4 Dry, filter and evaporate under reduced pressure. The crude mixture was purified by column chromatography on silica ge...

Embodiment 2

[0107] Synthesis of silanol and alcohol substrates

[0108]

[0109] Method D: Add nBuLi (2.5M in hexane, 1.1 equiv) dropwise to aryl bromide (1.0 equiv) in THF (0.5M) at -78°C under the protection of argon, and the mixture was cooled at -78°C After stirring for 1 h, chlorodimethylsilane (1.2 equiv) was added and the mixture was stirred at -78 °C for 1 h, then allowed to warm to room temperature and stirred overnight. Finally, the reaction mixture was heated at -78 °C with saturated NH 4 Quenched by Cl, after warming to room temperature, the mixture was filtered and washed with Et 2 Washed with O, the organic layers were combined, washed with MgSO 4 Drying, filtration, and evaporation under reduced pressure afforded the corresponding product, which was used in the next step without further purification.

[0110] Method E: Add KMnO to a solution of silane in THF (0.5M) under air atmosphere 4 (1.5 eq), the mixture was stirred at room temperature for 24 h, filtered through...

Embodiment 3

[0122] Screening of reaction conditions between dihydrosilane and silanol:

[0123] In the presence of Rh catalyst, tert-butyl(4-methoxyphenyl)silane 1a and dimethyl(phenyl)silanol 2a undergo intermolecular dehydrogenation Si-O coupling reaction at room temperature in toluene solvent, Tried several chiral diphosphine ligands, using [Rh(cod)Cl] 2 (1mol%) as the catalyst and Josiphos L1 (2.2mol%) as the chiral ligand, the siloxane product 3a was successfully obtained in 36% yield with good enantiomeric control (ee was 74%), others with different electronic The characteristic Josiphos-type ligands (L2 and L3) are also viable ligands.

[0124] The yield and enantioselectivity were significantly improved (68% yield, 97% ee) by using the Josiphos ligand L4 with the interchanged substituents of the phosphorus atom. Further screening of chiral ligands revealed that BINAP L5 and Segphos L6 were also effective for this reaction.

[0125] With L4 ligand, the common solvents DCE (1,2-d...

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Abstract

The invention belongs to the field of chiral silicon synthesis, and discloses a silicon-center chiral silicon-oxygen compound. The compound has a structure represented by general formula I shown in the specification. In the formula I, X is Si(R<3>)n or a formula also shown in the specification, R<1> is selected from alkyl, cycloalkyl and aryl, R<2> is selected from alkyl, substituted phenyl and aryl, R<3> is selected from alkyl, phenyl and substituted phenyl, n is 3, the three R<3> are the same or different, R<4> is selected from hydrogen and (C1-C4) alkyl, m is selected from 0, 1, 2 and 3, and Y is selected from substituted phenyl, substituted pyrenyl, aryl, heteroaryl and cycloalkyl. The invention also discloses a preparation method of the compound. Various highly functionalized chiral siloxanes and silyl ethers are obtained with good chemical, regional and stereo control and high yield, the variety of silicon center chiral compounds is expanded, and the method has the advantages of high enantioselectivity, wide substrate application range, mild reaction conditions, atom economy and the like. In addition, the compound provided by the invention has a huge application prospect in chiral organic photoelectric materials.

Description

technical field [0001] The invention belongs to the field of chiral silicon synthesis, in particular to a silicon-centered chiral silicon-oxygen compound and a preparation method thereof. Background technique [0002] Silicon-containing molecules are widely used in many fields and are of great significance in academia and industry. Over the past few decades, methods for the synthesis of novel organosilicon compounds have been developed, enabling the widespread use of silicon-containing molecules in organic, organometallic, and polymer chemistry. Among them, siloxane and silyl ether are important structures of silicon-based materials and can be used as protective groups, reagents and intermediates in organic synthesis. Although there are many methods for synthesizing siloxanes and silyl ethers, there are few reports on methods for obtaining chiral center compounds, which limits the design and application of chiral silicon compounds. [0003] At present, chiral silyl ethers ...

Claims

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Application Information

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IPC IPC(8): C07F7/18C07F7/08C07F7/10
CPCC07F7/0838C07F7/1804C07F7/0874C07F7/188Y02P20/55
Inventor 何川朱洁峰陈书友
Owner SOUTH UNIVERSITY OF SCIENCE AND TECHNOLOGY OF CHINA
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