The dicobaltoctacarbonyl catalyzed polymerization of allylic ethers
作者:James V. Crivello、Surésh K. Rajaraman
DOI:10.1016/s0040-4020(97)00955-1
日期:1997.11
Allylic ethers undergo spontaneous, exothermic polymerization in the presence catalytic amounts of dicobaltoctacarbonyl and silanes. Investigation of the mechanism of this new polymerization reaction indicates that the polymerization occurs by a multistep mechanism involving first, isomerization of the allylic ether to the corresponding 1-propenyl ether, then cationic polymerization of this latter
Conversions of alkyl allyl and terpenoid allyl ethers in a superbasic medium (dimethyl sulfoxide-potassium hydroxide) are studied. The ethers with an unbranched alkyl substituent isomerize into propenyl ethers, the ethers with a branched unsaturated substituent decompose to give a hydrocarbon, and diallyl ethers isomerize into allyl vinyl ethers whose Claisen rearrangement gives rise to aldehydes.
Gallium Tribromide Catalyzed Coupling Reaction of Alkenyl Ethers with Ketene Silyl Acetals
作者:Yoshihiro Nishimoto、Hiroki Ueda、Makoto Yasuda、Akio Baba
DOI:10.1002/anie.201203778
日期:2012.8.6
couple: The α‐alkenylation of esters was accomplished by GaBr3‐catalyzed coupling between alkenyl ethers and ketene silyl acetals. In this reaction system, various alkenyl ethers, including those with vinyl and substituted alkenyl groups, were applicable, and the scope of applicable ketene silyl acetals was sufficiently broad. The mechanism is also discussed.