376353-50-3Relevant articles and documents
Application of palladium-catalyzed allylic arylation to the synthesis of a (±)-7-deoxypancratistatin analogue
Shukla, Krupa H.,Boehmler, Debra J.,Bogacyzk, Suzanne,Duvall, Bridget R.,Peterson, William A.,McElroy, William T.,DeShong, Philip
, p. 4183 - 4186 (2006)
(Chemical Equation Presented) Palladium-catalyzed coupling of an aryl siloxane and an allylic carbonate proceeded in good yield to give an adduct that was converted to an analogue of (±)-7-deoxypancratistatin.
Rhodium(III)-Catalyzed Direct C-H Arylation of Various Acyclic Enamides with Arylsilanes
Li, Xiaolan,Sun, Kai,Shen, Wenjuan,Zhang, Yong,Lu, Ming-Zhu,Luo, Xuzhong,Luo, Haiqing
supporting information, p. 31 - 36 (2021/01/09)
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.
The Hiyama Cross-Coupling Reaction at Parts Per Million Levels of Pd: In Situ Formation of Highly Active Spirosilicates in Glycol Solvents
Ichii, Shun,Hamasaka, Go,Uozumi, Yasuhiro
supporting information, p. 3850 - 3854 (2019/11/11)
A palladium NNC-pincer complex at a 5 mol ppm loading efficiently catalyzed the Hiyama coupling reaction of aryl bromides with aryl(trialkoxy)silanes in propylene glycol to give the corresponding biaryls in excellent yields. This method was applied to the syntheses of adapalene and a biaryl-type liquid-crystalline compound, as well as to the derivatization of dextromethorphan and norfloxacin. ESI-MS and NMR analyses of the reaction mixture suggested the formation of pentacoordinate spirosilicate intermediates in situ. Preliminary theoretical studies revealed that the glycol-derived silicate intermediates formed in situ are quite reactive silicon reagents in the transmetalation step.
Rhodium(I)-catalyzed synthesis of aryltriethoxysilanes from arenediazonium tosylate salts with triethoxysilane
Tang, Zhi Yong,Zhang, Yuan,Wang, Tao,Wang, Wei
supporting information; experimental part, p. 804 - 808 (2010/06/14)
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.
A facile and efficient synthesis of aryltriethoxysilanes via sonochemical Barbier-type reaction
Lee, Adam Shih-Yuan,Chang, Yu-Ting,Chu, Shu-Fang,Tsao, Kuo-Wei
, p. 7085 - 7087 (2007/10/03)
A series of aryltriethoxysilanes was synthesized from the reaction mixture of aryl bromide, Mg powder, 1,2-dibromoethane and tetraethyl orthosilicate in THF under ultrasound. This sonochemical Barbier-type reaction provides a simple and efficient method for preparation of aryltriethoxysilanes. The Hiyama cross-coupling reaction of phenyltriethoxysilane with bromobenzene was investigated under different palladium catalysts and Pd(PhCN)2Cl2 was found to be the best choice.
Improved synthesis of aryltrialkoxysilanes via treatment of aryl Grignard or lithium reagents with tetraalkyl orthosilicates
Manoso, Amy S.,Ahn, Chuljin,Soheili, Arash,Handy, Christopher J.,Correia, Reuben,Seganish, W. Michael,DeShong, Philip
, p. 8305 - 8314 (2007/10/03)
General reaction conditions for the synthesis of aryl(trialkoxy)silanes from aryl Grignard and lithium reagents and tetraalkyl orthosilicates (Si(OR)4) have been developed. Ortho-, meta-, and para-substituted bromoarenes underwent efficient metalation and silylation at low temperature to provide aryl siloxanes. Mixed results were obtained with heteroaromatic substrates: 3-bromothiophene, 3-bromo-4-methoxypyridine, 5-bromoindole, and N-methyl-5-bromoindole underwent silylation in good yield, whereas a low yield of siloxane was obtained from 2-bromofuran, and 2-bromopyridine failed to give silylated product. The synthesis of siloxanes via organolithium and magnesium reagents was limited by the formation of di- and triarylated silanes (Ar 2Si(OR)2 and Ar3SiOR, respectively) and dehalogenated (Ar-H) byproducts. Silylation at low temperature gave predominantly monoaryl siloxanes, without requiring a large excess of the electrophile. Optimal reaction conditions for the synthesis of siloxanes from aryl Grignard reagents entailed addition of arylmagnesium reagents to 3 equiv of tetraethyl- or tetramethyl orthosilicate at -30 °C in THF. Aryllithium species were silylated using 1.5 equiv of tetraethyl- or tetramethyl orthosilicate at -78 °C in ether.
Improved synthesis of aryltriethoxysilanes via palladium(O)-catalyzed silylation of aryl iodides and bromides with triethoxysilane
Manoso,DeShong
, p. 7449 - 7455 (2007/10/03)
The scope of the palladium-catalyzed silylation of aryl halides with triethoxysilane has been expanded to include aryl bromides. A more general Pd(0) catalyst/ligand system has been developed that activates bromides and iodides: palladium(O) dibenzylideneacetone (Pd(dba)2) is activated with 2-(di-tert-butylphosphino)biphenyl (Buchwald's ligand) (1:2 mol ratio of Pd/phosphine). Electronrich para- and meta-substituted aryl halides (including unprotected aniline and phenol derivatives) undergo silylation to form the corresponding aryltriethoxysilane in fair to excellent yield; however, ortho-substituted aryl halides failed to be silylated.
