1286796-53-9Relevant academic research and scientific papers
Synthesis of α-trifluoromethylated amides by Eschenmoser-Claisen-type rearrangement of allylic alcohols
Walkowiak, Justyna,Tomas-Szwaczyk, Magdalena,Koroniak, Henryk,Haufe, Guenter
, p. 189 - 197,9 (2020/07/31)
A new, mild method to prepare α-trifluoromethylated amides bearing an additional trans-configured double bond in γ-position is described. Treatment at room temperature of fluorinated and non-fluorinated allylic alcohols 1 and 2 with the 1,1,3,3,3-pentafluoropropene-diethylamine adduct (PFPDEA) in the presence of triethylamine as base gave the products of [3,3]-sigmatropic Eschenmoser-Claisen-type rearrangements with good yields and excellent diastereoselectivity due to chair-like conformations of transition states. Starting with enantiomerically enriched allylic alcohols chirality transfer from carbon 3 of the allylic system to carbon 2 of the final α-trifluoromethyl carboxamides was observed. This methodology was applied to both simple and more complex, including terpenic, allylic alcohols and might be developed to an alternative strategy to the well-known electrophilic α-trifluoromethylation of carbonyl compounds.
Palladium-catalyzed allylic fluorination
Hollingworth, Charlotte,Hazari, Amaruka,Hopkinson, Matthew N.,Tredwell, Matthew,Benedetto, Elena,Huiban, Mickael,Gee, Antony D.,Brown, John M.,Gouverneur, Veronique
supporting information; experimental part, p. 2613 - 2617 (2011/05/03)
Mild and rapid: The title reaction is presented and its applicability to 18F radiolabeling is demonstrated (see scheme; TBAF=tetra-n- butylammonium fluoride, THF=tetrahydrofuran, dba=dibenzylideneacetone). The use of p-nitrobenzoate as the leaving group is significant to the success of this catalytic organometallic fluorination process. A range of allylic fluorides were synthesized by this method. Copyright
