ORGN 53 |
Synthetic applications of vinyl tris(trimethylsilyl)silanes
| Pedro I. Garcia Jr., Zhizhong Wang, and Stanislaw F. Wnuk. Department of Chemistry and Biochemistry, Florida International University, Miami, FL 33199 |
Stereoselective radical-mediated silyldesulfonylations of vinyl sulfones 1(E) with tris(trimethylsilyl)silane/AIBN produced various vinyl silanes 2(E) in high yields. Successive treatment of 2 (E, R=Ph or PhCH2CH2) with H2O2 in basic aqueous solution, followed by addition of Pd(PPh3)4 and iodobenzene gave cross-coupling product 3 (E, 86% or 58%). Apparently, hydrogen peroxide cleaves Si-Si bond(s) to generate silanols type of intermediates, which are known to be good substrates for Hiyama coupling (Denmark and Sweis, Acc. Chem. Res. 2002, 35, 835). Tamao-Kumada oxidation of 2 (R=Ph; H2O2/KF/NaHCO3/MeOH/H2O) produced homologated benzaldehyde 4. Other synthetic applications of vinyl and (a-fluoro)vinyl tris(trimethylsilyl)silanes will be also presented. |
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New Reactions and Methodology, Metal-Mediated Reactions, Heterocycles and Aromatics
8:00 PM-10:00 PM, Sunday, March 28, 2004 Anaheim Convention Center -- Hall A, Poster
Division of Organic Chemistry
The 227th ACS National Meeting, Anaheim, CA, March 28-April 1, 2004
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