883547-73-7Relevant academic research and scientific papers
A NOVEL PROCESS FOR THE SYNTHESIS OF 1-ARYL-1-TRIFLUOROMETHYLCYCLOPROPANES
-
Page/Page column 18, (2018/08/26)
The present invention relates to a process for the manufacturing of 1-aryl-1-trifluoromethylcyclopropanes, which serve as intermediates for the manufacturing of calcium T channel blockers of the general formula (A) which are described in WO 2015/186056.
1,3-γ-Silyl-elimination in electron-deficient cationic systems
Mercadante, Michael A.,Kelly, Christopher B.,Hamlin, Trevor A.,Delle Chiaie, Kayla R.,Drago, Michael D.,Duffy, Katherine K.,Dumas, Megan T.,Fager, Diana C.,Glod, Bryanna L. C.,Hansen, Katherine E.,Hill, Cameron R.,Leising, Rebecca M.,Lynes, Catherine L.,Macinnis, Allyson E.,McGohey, Madeline R.,Murray, Stephanie A.,Piquette, Marc C.,Roy, Shaina L.,Smith, Ryan M.,Sullivan, Katherine R.,Truong, Bao H.,Vailonis, Kristina M.,Gorbatyuk, Vitaliy,Leadbeater, Nicholas E.,Tilley, Leon J.
, p. 3983 - 3994 (2014/10/15)
Placement of an electron-withdrawing trifluoromethyl group (-CF 3) at a putative cationic centre enhances γ-silyl neighbouring-group participation (NGP). In stark contrast to previously studied γ-silyl-substituted systems, the preferred reaction pathway is 1,3-γ-silyl elimination, giving ring closure over solvent substitution or alkene formation. The scope of this cyclopropanation reaction is explored for numerous cyclic and acyclic examples, proving this method to be a viable approach to preparing CF3-substituted cyclopropanes and bicyclic systems, both containing quaternary centres. Rate-constants, kinetic isotope effects, and quantum mechanical calculations provided evidence for this enhancement and further elaborated the disparity in the reaction outcome between these systems and previously studied γ-silyl systems.
