376353-52-5Relevant articles and documents
Ligand-promoted oxidative cross-coupling of aryl boronic acids and aryl silanes by palladium catalysis
Yu, Jingxun,Liu, Jun,Shi, Guangfa,Shao, Changdong,Zhang, Yanghui
supporting information, p. 4079 - 4082 (2015/03/30)
The first cross-coupling reaction between aryl silanes and aryl boronic acids is described. This transformation represents one of the very few examples of coupling reactions between two nucleophilic organometallic reagents and provides a new method for the formation of biaryl compounds. The successful development of this reaction was enabled by the use of commercially available 2,2-bis(diphenylphosphino)-1,1-binaphthyl (BINAP) as the ligand. A small amount of BINAP (3 mol %) was sufficient to suppress the formation of the homocoupling products, and the reaction yielded the cross-coupling products with high selectivity under mild conditions, even when the ratio of the two coupling partners was 1:1.
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.
Rhodium(I)-Catalyzed Silylation of Aryl Halides with Triethoxysilane: Practical Synthetic Route to Aryltriethoxysilanes
Murata, Miki,Ishikura, Masanori,Nagata, Masayuki,Watanabe, Shinji,Masuda, Yuzuru
, p. 1843 - 1845 (2007/10/03)
(Equation Presented) The specific silylation of aryl iodides and bromides with triethoxysilane (EtO)3SiH in the presence of NEt3 and a catalytic amount of [Rh-(cod)(MeCN)2]BF4 provides the corresponding aryltriethoxysilanes in high yield.
