Alkoxysilanes for C–C Coupling Reactions

Chemfiles Volume 3 Article 5

The use of silicon compounds as transmetalation reagents has attracted much attention as a viable alternative to the popular Stille and Suzuki coupling reactions mainly due to the formation of nontoxic byproducts and stability to many reaction conditions.1-4 Silicon-based coupling reactions can be carried out using aryl-, heteroaryl-, or alkenyl- halides and alkoxysilanes in the presence of palladium or rhodium catalysts. Among the various types of silicon compounds available, alkoxysilanes are more effective in coupling reactions.5-11

Silicon-based coupling scheme

Figure 1.Silicon-based coupling scheme

Recently, considerable attention has been paid to the rhodiumcatalyzed addition of aryl(trialkoxy)silanes to carbonyl compounds, such as aldehydes, α,β-unsaturated ketones and esters.12

Rhodium catalyzed scheme

Figure 2.Rhodium catalyzed scheme

Materials
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References

1.
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Mowery ME, DeShong P. 1999. Improvements in Cross Coupling Reactions of Hypervalent Siloxane Derivatives. Org. Lett.. 1(13):2137-2140. http://dx.doi.org/10.1021/ol991186d
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Murata M, Shimazaki R, Watanabe S, Masuda Y. 2001. Palladium-Catalyzed Cross-Coupling Reaction of Aryltriethoxysilanes with Aryl Bromides under Basic Aqueous Conditions. Synthesis. 2001(15):2231-2233. http://dx.doi.org/10.1055/s-2001-18435
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Oi S, Honma Y, Inoue Y. 2002. Conjugate Addition of Organosiloxanes to ?,?-Unsaturated Carbonyl Compounds Catalyzed by a Cationic Rhodium Complex. Org. Lett.. 4(4):667-669. http://dx.doi.org/10.1021/ol025518h

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