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Solvent-dependent chemoselectivities in Ce(IV)-mediated oxidative coupling reactions
Yang Zhang1, Andrew J Raines, Robert A Flowers
1Department of Chemistry and Biochemistry, Texas Tech University, Box 41061, Lubbock, TX 79423-1061, USA.
Organic Letters
|June 21, 2003
Summary
Researchers explored the oxidative coupling of carbonyl compounds with allyl trimethylsilane using CTAN. Solvent choice (acetonitrile vs. dichloromethane) dictated chemoselectivity, yielding allylation or dihydrofuran products.
Area of Science:
- Organic Chemistry
- Synthetic Chemistry
Background:
- Oxidative coupling reactions are crucial for C-C bond formation.
- 1,3-Diketones, beta-keto esters, and beta-keto silyl enol ethers are versatile synthetic building blocks.
- Allyl trimethylsilane is a valuable allylating reagent.
Purpose of the Study:
- To investigate the oxidative coupling of various carbonyl compounds with allyl trimethylsilane.
- To explore the effect of reaction conditions, specifically solvent, on chemoselectivity.
- To synthesize allylated products and dihydrofurans.
Main Methods:
- Oxidative coupling reaction utilizing CTAN as an oxidant.
- Employing 1,3-diketones, beta-keto esters, and beta-keto silyl enol ethers as substrates.
- Utilizing allyl trimethylsilane as the allyl source.
- Varying the solvent system between acetonitrile (CH3CN) and dichloromethane (CH2Cl2).
Main Results:
- Chemoselectivity was dependent on the solvent used.
- In acetonitrile, allylation products were predominantly formed.
- In dichloromethane, dihydrofuran products were obtained in good yields.
- The reaction demonstrated good yields for both observed pathways.
Conclusions:
- The choice of solvent significantly influences the chemoselectivity of the oxidative coupling reaction.
- This method provides a facile route to both allylated compounds and dihydrofurans from readily available starting materials.
- The reaction offers tunable synthesis of valuable organic molecules.