6145-81-9Relevant articles and documents
Vinyl polymerization versus [1,3] O to C rearrangement in the ruthenium-catalyzed reactions of vinyl ethers with hydrosilanes
Harada, Nari-Aki,Nishikata, Takashi,Nagashima, Hideo
supporting information; experimental part, p. 3243 - 3252 (2012/06/01)
Two reactions, vinyl polymerization and [1,3] O to C rearrangement of vinyl ethers, are investigated in the ruthenium-catalyzed reaction with hydrosilanes. The reaction pathways are dependent on the substituents of the vinyl ether, in particular, those of the alkoxy group. Primary-, secondary-, and tertiary-alkyl vinyl ethers, ROCHCH2, are polymerized with ease to give the corresponding polymer in good yields. When R is electron-donating benzyl groups, the reaction does not give the polyvinyl ether but results in [1,3] O to C rearrangement to give the corresponding aldehyde, RCH2CHO in moderate to good yields. The rearrangement selectively proceeds when vinyl ethers having α-substituents are used as the starting materials to give the corresponding ketones in high yields. With catalytic amounts of hydrosilanes, the rearrangement gives ketones or aldehydes selectively. In sharp contrast, use of excess amounts of hydrosilanes leads to the rearrangement followed by reduction of the formed carbonyl group to give the corresponding silyl ethers in good yields. Nature of catalytically active species is discussed. Crown Copyright
Conversions of allyl ethers in a superbasic medium
Vyglazov,Chuiko,Izotova
, p. 933 - 939 (2007/10/03)
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.
The dicobaltoctacarbonyl catalyzed polymerization of allylic ethers
Crivello, James V.,Rajaraman, Suresh K.
, p. 15167 - 15186 (2007/10/03)
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 species. It is proposed that two different cobalt-containing species are present which catalyze this tandem process.
