- Rhodium(III)-Catalyzed Direct C-H Arylation of Various Acyclic Enamides with Arylsilanes
-
The stereoselective β-C(sp2)-H arylation of various acyclic enamides with arylsilanes via Rh(III)-catalyzed cross-coupling reaction was illustrated. The methodology was characterized by extraordinary efficacy and stereoselectivity, a wide scope of substrates, good functional group tolerance, and the adoption of environmentally friendly arylsilanes. The utility of this present method was evidenced by the gram-scale synthesis and further elaboration of the product. In addition, Rh(III)-catalyzed C-H activation is considered to be the critical step in the reaction mechanism.
- Li, Xiaolan,Sun, Kai,Shen, Wenjuan,Zhang, Yong,Lu, Ming-Zhu,Luo, Xuzhong,Luo, Haiqing
-
supporting information
p. 31 - 36
(2021/01/09)
-
- A naphthyl alkoxyl silane preparation method
-
The invention relates to a preparation method of naphthyl alkoxysilane. The preparation method comprises the following steps: in an organic solvent, alkoxysilane, magnesium and 1-halogen naphthalene are mixed for Grignard reaction, so as to obtain the naphthyl alkoxysilane, wherein the alkoxysilane is selected from one of tetramethoxysilane, methyltrimethoxysilane, tetraethoxysilane and methyl triethoxysilane. In addition, the method further comprises purification treatment performed through mixing and heating the naphthyl alkoxysilane and an alkaline substance, and organic silicon resin prepared by using the naphthyl alkoxysilane as a raw material is high in transparency and excellent in aging resistance.
- -
-
Paragraph 0042; 0043; 0044; 0045; 0046
(2017/08/26)
-
- The method of manufacturing the silicon compound
-
PROBLEM TO BE SOLVED: To provide a method for producing a silicon compound having a polycyclic hydrocarbon group, at the synthesis step of which method a Grignard reagent is used and removal of a polycyclic hydrocarbon being a by-product is facilitated.SOLUTION: The method for producing the silicon compound is characterized in that a polyalkylene glycol dialkyl ether compound, which is shown by the formula:RO-R-ORand has the boiling point being within (the boiling point of the polycyclic hydrocarbon being the by-product)± 28°C, is added to the Grignard reagent shown by the formula:RMgY (in which Ris the polycyclic hydrocarbon group; Y is a halogen atom), the ether compound-added Grignard reagent is subjected to a coupling reaction with a silane compound shown by the formula:RSiX(in which Ris an aliphatic hydrocarbon group; X is a halogen atom or 1-5C alkoxy group; n is an integer of 0-3) to synthesize the silicon compound, which is shown by the formula:RRSiXand has the polycyclic hydrocarbon group, the polycyclic hydrocarbon and the polyalkylene glycol dialkyl ether compound are removed simultaneously by distillation, and the synthesized silicon compound is distilled.
- -
-
Paragraph 0064-0066; 0085-0087
(2017/05/06)
-
- In Situ Generation of ArCu from CuF2 Makes Coupling of Bulky Aryl Silanes Feasible and Highly Efficient
-
A bimetallic system of Pd/CuF2, catalytic in Pd and stoichiometric in Cu, is very efficient and selective for the coupling of fairly hindered aryl silanes with aryl, anisyl, phenylaldehyde, p-cyanophenyl, p-nitrophenyl, or pyridyl iodides of conventional size. The reaction involves the activation of the silane by CuII, followed by disproportionation and transmetalation from the CuI(aryl) to PdII, upon which coupling takes place. CuIII formed during disproportionation is reduced to CuI(aryl) by excess aryl silane, so that the CuF2 system is fully converted into CuI(aryl) and used in the coupling. Moreover, no extra source of fluoride is needed. Interesting size selectivity towards coupling is found in competitive reactions of hindered aryl silanes. Easily accessible [PdCl2(IDM)(AsPh3)] (IDM = 1,3-dimethylimidazol-2-ylidene) is by far the best catalyst, and the isolated products are essentially free from As or Pd (2: In the Cu-promoted Hiyama process, CuF2 plays the role of two reagents to provide full conversion into the fluoride and copper is also required to transform bulky trialkoxysilanes in situ into CuAr. CuAr immediately transmetalates to Pd, which makes the otherwise inaccessible Pd-catalyzed coupling of bulky arylsilanes feasible and highly efficient.
- Delpozo, Juan,Casares, Juan A.,Espinet, Pablo
-
supporting information
p. 4274 - 4284
(2016/03/16)
-
- Method for preparing naphthyl alkoxy silane monomers
-
The invention relates to a method for preparing naphthyl alkoxy silane monomers. The method comprises the following step: mixing alkoxy silane, sodium and 1-naphthalene halide to be reacted to obtain naphthyl alkoxy silane in an organic solvent, wherein the alkoxy silane is selected any one of tetramethoxysilane, methyltrimethoxysilane, tetraethoxysilane and methyl triethoxysilane. The method is easy to operate.
- -
-
Paragraph 0022; 0023
(2017/04/27)
-
- Meerwein's reagent mediated, significantly enhanced nucleophilic fluorination on alkoxysilanes
-
We developed a new facile method to fluorosilanes from alkoxysilanes using Meerwein's reagent. Our protocol afforded fluorosilanes in excellent yields in various organic solvents including acetonitrile under mild reaction conditions at room temperature. We also proposed a reaction mechanism with the probable silyloxonium intermediates. Georg Thieme Verlag Stuttgart · New York.
- Jorapur, Yogesh R.,Shimada, Toyoshi
-
supporting information; experimental part
p. 1064 - 1068
(2012/06/17)
-
- Rhodium(I)-catalyzed synthesis of aryltriethoxysilanes from arenediazonium tosylate salts with triethoxysilane
-
An efficient method for the preparation of aryltriethoxy-silanes from arenediazonium tosylate salts has been developed, which expands the substrates of rhodium-catalyzed silylation from iodides, bromides, and triflates to diazonium salts. A new method for hydrodediazoniation has also been explored.
- Tang, Zhi Yong,Zhang, Yuan,Wang, Tao,Wang, Wei
-
supporting information; experimental part
p. 804 - 808
(2010/06/14)
-
- Covalent Attachment of Arenes to SnO2-Semiconductor Electrodes
-
The synthesis and chemical and physical properties of some arene-derivatized tin oxide semiconductor electrodes are described.Several techniques for attachment are employed (esterification, silanation, silanation/amidation, and the use of cyanuric chloride as a linking agent) and the merits of each are evaluated.The relationship between the observed properties of the attached arenes and the potential utility of the derivatized electrodes as anodes in photogalvanic cells is discussed.
- Fox, Marye Anne,Nobs, Frederic J.,Voynick, Tamara A.
-
p. 4029 - 4036
(2007/10/02)
-