1541177-31-4Relevant academic research and scientific papers
Palladium-Catalyzed Trimethylenemethane Cycloaddition of Olefins Activated by the δ-Electron-Withdrawing Trifluoromethyl Group
Trost, Barry M.,Debien, Laurent
, p. 11606 - 11609 (2015)
α-Trifluoromethyl-styrenes, trifluoromethyl-enynes, and dienes undergo palladium-catalyzed trimethylenemethane cycloadditions under mild reaction conditions. The trifluoromethyl group serves as a unique δ-electron-withdrawing group for the activation of the olefin toward the cycloaddition. This method allows for the formation of exomethylene cyclopentanes bearing a quaternary center substituted by the trifluoromethyl group, compounds of interest for the pharmaceutical, agrochemical, and materials industries. In the diene series, the cycloaddition operates in a [3 + 4] and/or [3 + 2] manner to give rise to seven- and/or five-membered rings. This transformation greatly improves the scope of the TMM cycloaddition technology and provides invaluable insights into the reaction mechanism.
Methylenation of perfluoroalkyl ketones using a Peterson olefination approach
Hamlin, Trevor A.,Kelly, Christopher B.,Cywar, Robin M.,Leadbeater, Nicholas E.
, p. 1145 - 1153 (2014/03/21)
An operationally simple, inexpensive, and rapid route for the olefination of a wide array of trifluoromethyl ketones to yield 3,3,3- trifluoromethylpropenes is reported. Using a Peterson olefination approach, the reaction gives good to excellent yields of the alkene products and can be performed without purification of the β-hydroxysilyl intermediate. The reaction can be extended to other perfluoroalkyl substituents and is easily scaled up. The alkenes prepared can be readily transformed into a variety of other perfluoroalkyl-containing compounds.
A continuous-flow approach to 3,3,3-trifluoromethylpropenes: Bringing together grignard addition, peterson elimination, inline extraction, and solvent switching
Hamlin, Trevor A.,Lazarus, Gillian M. L.,Kelly, Christopher B.,Leadbeater, Nicholas E.
supporting information, p. 1253 - 1258 (2014/12/10)
A continuous-flow approach to the synthesis of 3,3,3-trifluoromethylpropenes involving Grignard addition of (trimethylsilyl)methylmagnesium chloride to a trifluoromethyl ketone followed by dehydrative desilylation of the α-tri fluoromethyl-β-hydroxysilyl alcohol using trimethylsilyl tri fluoromethanesulfonate is reported. An inline aqueous/organic extraction and a concomitant solvent switch were key to the success of the methodology. Transition from batch to continuous flow conditions allows for higher yields, shorter reaction times, and facile scale out.
