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 et

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

Example Embodiment

[0086] Example 1

[0087] Synthesis of dihydrosilane substrate

[0088]

[0089] Method A: TBULi (1.3M pentane solution, 1.1 equivalents) were added dropwise to the aryl bromide (1.0 equivalent) of THF (0.5 m) solution under -78 ° C, argon, and stirred at -78 ° C 1h, then add TBusicl in 10ml THF 3 (1.2 equivalents). The mixture was stirred at -78 ° C for 1 h, then warmed to room temperature and stirred overnight. Cooling the reaction again to -78 ° C and dropped with LiAlh 4 (2.5 m THF solution, 2.0 equivalents), and stirred at -78 ° C for 30 min, then the mixture was hot to room temperature and stirred for 8 h. Finally, the reaction mixture is saturated at -78 ° C NH. 4 Cl to quench, increase the mixture after rising to room temperature, use ET 2 O Wash, combine organic layers and use MGSO 4 Dry, filtrate, evaporate under reduced pressure. The crude mixture was purified by silica gel column chromatography (100% petroleum ether) to give dihydrosilane.

[0090]

[0091] Method ...

Example Embodiment

[0106] Example 2

[0107] Synthesis of silanol and alcohol substrate

[0108]

[0109] Method D: NBULI (2.5 m hexane solution, 1.1 equivalents) was added dropwise to the aryl bromide (1.0 equivalend) at -78 ° C, argon (0.5 m) solution, and mixture at -78 ° C. The mixture was stirred for 1 h, and the chlorine diimethylsilane (1.2 equivalents) was added, and the mixture was stirred at -78 ° C for 1 h, then warmed to room temperature and stirred overnight. Finally, the reaction mixture is saturated at -78 ° C. 4 CL quenching, after rising to room temperature, filtrate the mixture, use ET 2 O Wash, combine organic layers, with MGSO 4 Dry, filtration, evaporation and evaporation were evaporated, and the corresponding product was obtained directly for the next step without further purification.

[0110] Method E: In the air atmosphere, add KMNO to the silane in THF (0.5 m) solution 4 (1.5 equivalents), the mixture is stirred at room temperature for 24 h, filtered through the short sil...

Example Embodiment

[0121] Example 3

[0122] NETATISTRY: Dihydrosilane and silanols Screening:

[0123] In the presence of a RH catalyst, the tert-butyl (4-methoxyphenyl) silane 1A was carried out by the dimethyl (phenyl) silanol 2a, and the molecular dehydrogenated Si-O reacted reaction was carried out at room temperature, toluene solvent, Try several chiral phosphine ligands, using [RH (COD) Cl] 2 (1 mol%) As the catalyst and JosiPHOS L1 (2.2 mol%) as a chiral ligand, the silicone product 3a is successfully obtained, the yield is 36%, the enantiomer is good (EE is 74%), and other electrons have different electrons Features Josiphos-type ligands (L2 and L3) are also feasible ligands.

[0124] The JosiPhos ligand L4, yield, and no-selectivity of the substituent using the phosphorus atom (68% yield, 97% EE) were significantly increased. Further screening of the counterpart ligand found that BinaP L5 and Segphos L6 also valid for the reaction.

[0125] Using L4 ligands, common solvent DCE (1,2-dichlor...

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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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