Rhodium(I)-Catalyzed Silylation of Aryl Halides with Triethoxysilane: Practical Synthetic Route to Aryltriethoxysilanes
Miki Murata*, Masanori Ishikura, Masayuki Nagata, Shinji Watanabe and Yuzuru Masuda
*Department of Materials Science, Kitami Institute of Technology, Kitami
090-8507, Japan, Email: muratamk
mail.kitami-it.ac.jp
M. Murata, M. Ishikura, M. Nagata, S. Watanabe, Y. Masuda, Org. Lett., 2002, 4, 1843-1845.
DOI: 10.1021/ol025770p
Abstract
A mild and selective 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 aryltriethoxysilanes in high yield.
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Details
The document discusses a study on the rhodium(I)-catalyzed silylation of aryl halides with triethoxysilane to produce aryltriethoxysilanes. This method offers a practical synthetic route, providing high yields and overcoming limitations of previous methods that often resulted in undesirable byproducts. The reaction involves using [Rh(cod)(MeCN)2]BF4 as a catalyst and NEt3 as a base in DMF solvent. The process is effective for aryl iodides and bromides, including those with electron-withdrawing groups, and is less sensitive to electronic and steric hindrances compared to palladium-catalyzed methods. The study also highlights the importance of iodide ions in improving the reaction's selectivity and yield. The proposed mechanism involves the formation of a silyl rhodium(I) complex, followed by oxidative addition of the aryl halide and reductive elimination to produce the desired product. This method provides a simple and efficient way to synthesize aryl(triethoxy)silanes, which are valuable intermediates in organic synthesis. The research is ongoing to further understand the mechanism and explore silylation of other organic halides. Experimental procedures and spectroscopic data are available online.
M. Murata, K. Ota, H. Yamasaki, S. Watanabe, Y. Masuda, Synlett, 2007, 1387-1390.
M. Murata, R. Shimazaki, S. Watanabe, Y. Masuda, Synthesis, 2001, 2231-2233.
Key Words
ID: J54-Y2002-560
