908608-90-2Relevant academic research and scientific papers
HFO-1234yf as a CF3-Building Block: Synthesis and Chemistry of CF3-Ynones
Murray, Ben J.,Marsh, Thomas G. F.,Yufit, Dmitri S.,Fox, Mark A.,Harsanyi, Antal,Boulton, Lee T.,Sandford, Graham
supporting information, p. 6236 - 6244 (2020/09/15)
Reaction of low cost, readily available 4th generation refrigerant gas 2,3,3,3-tetrafluoropropene (HFO-1234yf) with lithium diisopropylamide (LDA) leads to formation of lithium 3,3,3-trifluoropropynide, addition of which to a range of aldehydes formed CF3-alkynyl alcohol derivatives on multigram scale, which were oxidised using Dess–Martin periodinane (DMP) to give substituted CF3-ynones with minimal purification required. Michael-type additions of alcohol and amine nucleophiles to CF3-ynones are rapid and selective, affording a range of CF3-enone ethers and enaminones in excellent yields with high stereoselectivity for the Z-isomer. By analogous reactions with difunctional nucleophiles, a wide range of CF3-substituted pharmaceutically relevant heterocyclic structures can be accessed, exemplified in the simple synthesis of the anti-arthritis drug celecoxib from HFO-1234yf in just three steps.
Highly regio- and stereoselective hydrosilylation of β-fluoroalkylated α,β-unsaturated ketones
Ikeda, Natsumi,Konno, Tsutomu
, p. 69 - 76 (2015/03/18)
Treatment of β-fluoroalkylated α,β-unsaturated ketones with 10.2 equiv of triethylsilane in the presence of 3 mol% of Co2(CO)8 in dichloroethane at the reflux temperature for 4 h gave 1,4-hydrosilylated adducts in a highly regio- and
Stereospecific asymmetric N-heterocyclic carbene (NHC)-catalyzed redox synthesis of trifluoromethyl dihydropyranones and mechanistic insights
Davies, Alyn T.,Taylor, James E.,Douglas, James,Collett, Christopher J.,Morrill, Louis C.,Fallan, Charlene,Slawin, Alexandra M. Z.,Churchill, Gwydion,Smith, Andrew D.
, p. 9243 - 9257 (2013/10/08)
N-Heterocyclic carbene (NHC)-catalyzed redox asymmetric hetero-Diels-Alder reactions of α-aroyloxyaldehydes with β-trifluoromethyl enones generates synthetically useful dihydropyranones containing a stereogenic trifluoromethyl substituent in good yields (up to 81%) and excellent diastereoselectivity and enantioselectivity (up to >95:5 dr and >99% ee). The process is stereospecific, with use of either (E)- or (Z)-β- trifluoromethyl enones forming syn- or anti-dihydropyranone products, respectively. Mechanistic studies through in situ kinetic analysis of the reaction reveal key differences in reactivity between chiral NHC precursor 1 and an achiral NHC precursor.
Preparation of CF3-containing 1,3-Di- and 1,1,3-trisubstituted allenes
Yamazaki, Takashi,Yamamoto, Takahiro,Ichihara, Ritsuko
, p. 6251 - 6253 (2007/10/03)
Novel synthetic pathway to access trifluoromethylated allenes with 1,3-di- as well as 1,1,3-trisubstitution patterns was developed from a variety of 4,4,4-trifluorobut-2-yn-1-ols which were then transformed into the corresponding vinylic iodides in highly
