21701-61-1Relevant academic research and scientific papers
Silicon-center chiral silicon-oxygen compound and preparation method thereof
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Paragraph 0086; 0100-0103; 0105, (2021/07/24)
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)n or a formula also shown in the specification, R is selected from alkyl, cycloalkyl and aryl, R is selected from alkyl, substituted phenyl and aryl, R is selected from alkyl, phenyl and substituted phenyl, n is 3, the three R are the same or different, R 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.
Catalytic Enantioselective Dehydrogenative Si-O Coupling to Access Chiroptical Silicon-Stereogenic Siloxanes and Alkoxysilanes
Zhu, Jiefeng,Chen, Shuyou,He, Chuan
supporting information, p. 5301 - 5307 (2021/05/04)
A rhodium-catalyzed enantioselective construction of triorgano-substituted silicon-stereogenic siloxanes and alkoxysilanes is developed. This process undergoes a direct intermolecular dehydrogenative Si-O coupling between dihydrosilanes with silanols or alocohols, giving access to a variety of highly functionalized chiral siloxanes and alkoxysilanes in decent yields with excellent stereocontrol, that significantly expand the chemical space of the silicon-centered chiral molecules. Further utility of this process was illustrated by the construction of CPL-active (circularly polarized luminescence) silicon-stereogenic alkoxysilane small organic molecules. Optically pure bis-alkoxysilane containing two silicon-stereogenic centers and three pyrene groups displayed a remarkable glum value with a high fluorescence quantum efficiency (glum = 0.011, φF = 0.55), which could have great potential application prospects in chiral organic optoelectronic materials.
Electrochemical properties of arylsilanes
Biedermann, Judith,Wilkening, H. Martin R.,Uhlig, Frank,Hanzu, Ilie
, p. 13 - 18 (2019/03/27)
In the past, the electrochemical properties of organosilicon compounds were investigated for both fundamental reasons and synthesis purposes. Little is, however, known about the electrochemical behaviour of hydrogen-bearing arylsilanes. Here, we throw light on the electrochemical properties of 11 arylsilanes compounds, 2 of them synthesized for the first time. The oxidation potentials are found to depend on both the nature and number of the aryl groups. Based on these findings it was possible to establish some variation trends that match the expected structure–property correlations. Furthermore, we present first insights into the electrochemical reaction kinetics behind and identify several soluble electrochemical oxidation products.
Silylation of Aryl Halides with Monoorganosilanes Activated by Lithium Alkoxide
Yoshida, Takumi,Ilies, Laurean,Nakamura, Eiichi
supporting information, p. 2844 - 2847 (2018/05/29)
Lithium alkoxide activates a monoorganosilane to generate a transient LiH/alkoxysilane complex, which quickly reacts with aryl and alkenyl halides at 25 °C to deliver a diorganosilane product. Experimental and theoretical studies suggest that the reaction includes nucleophilic attack of LiH on the halogen atom of the organic halide to generate a transient organolithium/alkoxysilane intermediate, which undergoes quick carbon-silicon bond formation within the complex.
Acceleration of the substitution of silanes with Grignard reagents by using either LiCl or YCl3/MeLi
Hirone, Naoki,Sanjiki, Hiroaki,Tanaka, Ryoichi,Hata, Takeshi,Urabe, Hirokazu
supporting information; experimental part, p. 7762 - 7764 (2010/12/25)
Getting up to speed: Both LiCl and the YCl3/MeLi catalyst system have an acceleration effect upon the substitution of silanes using Grignard reagents (see scheme). The method provides access to benzyl-, allyl-, and arylsilanes in good yields from the starting silanes.
Iridium(III)-catalyzed enantioselective Si-H bond insertion and formation of an enantioenriched silicon center
Yasutomi, Yoichi,Suematsu, Hidehiro,Katsuki, Tsutomu
supporting information; experimental part, p. 4510 - 4511 (2010/06/19)
Iridium(III)-salen complexes were found to efficiently catalyze enantioselective carbene Si-H bond insertion. Highly enantioselective Si-H insertion with α-alkyl- α-diazoacetates (≥97% ee) was achieved for the first time by using the iridium complex 4 {(aR,S), Ar = 4-TBDPSC 6H4} bearing a concave-shaped salen ligand as the catalyst. Formation of a chiral silicon center was also achieved for the first time by the Si-H insertion into prochiral silanes: the reactions between prochiral silanes and tert-butyl α-diazopropionate in the presence of complex 5 {(aR,S), Ar = Ph} proceeded with high stereoselectivity (84-99% de, 94→99% ee). The Si-H insertion into trisubstitued silanes with α-aryl- α-diazoacetates proceeded with almost complete enantioselectivity (≥99% ee) by using complex 1 {(aR,R), Ar = Ph} as catalyst.
