Palladium-catalyzed preparation of α-allyl esters and α,β-unsaturated esters from saturated esters via their silyl acetals

✍ Scribed by Jro Tsuji; Kazuhiko Takahashi; Ichiro Minami; Isao Shimizu

• Publisher: Elsevier Science
• Year: 1984
• Tongue: French
• Weight: 198 KB
• Volume: 25
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)81518-5

✦ Synopsis

Reaction of ketene silyl acetals with allylic carbonates in the presence of palladium-phosphine catalyst in dioxane gives a-ally1 esters in high yields.

When the reaction is carried out with phosphine-free palladium catalyst in nitriles,cl,fi-unsaturated esters are obtained in good yields.

We have reported an efficient method for allylation of ketones and aldehydes by the palladium-catalyzed reaction of silyl enol ethers with allylic carb0nates.l) Also a,B-unsaturated ketones and aldehydes are prepared by using nitriles as the solvents.2) Unlike silyl enol ethers which are used extensively in organic synthesis, ketene silyl acetals have rather limited use because