1522-41-4Relevant articles and documents
Acetyl Hypofluorite, a New Moderating Carrier of Elemental Fluorine and Its Use in Fluorination of 1,3-Dicarbonyl Derivatives
Lerman, Ori,Rozen, Shlomo
, p. 724 - 727 (1983)
Elemental fluorine and most of the fluoroxy reagents do not react efficiently or cleanly with 1,3-dicarbonyl derivatives or with their corresponding metal enolates even at -75 degC.It has been found that a suspension of sodium acetate in CFCl3 or in CFCl3-AcOH, when treated with elemental fluorine, forms a new electrophilic fluorinating reagent, CH3COOF (1), which reacts with substrates without further isolation or purification.This reagent is milder than F2, CF3OF, or CF3COOF and reacts successfully where the other reagents fail.When 1 reacts with 1,3-dicarbonyl compounds, the main product is the 1,3-dioxo-2-fluoro derivative in reasonable yields.When, however, the corresponding sodium enolates were treated with 1, the yields of the monofluoro derivatives were considerably higher.In the case of 1,3-dicarbonyl derivatives with low enol content, only the sodium enolates react with 1 to produce good to very good yields of the corresponding 2-monofluoro derivatives.Thus 1 can be considered as a moderating carrier of the highly reactive F2.
One-pot fluorination and organocatalytic Robinson annulation for asymmetric synthesis of mono- and difluorinated cyclohexenones
Huang, Xin,Zhao, Weizhao,Zhang, Xiaofeng,Liu, Miao,Vasconcelos, Stanley N.S.,Zhang, Wei
, (2018)
A one-pot fluorination and organocatalytic Robinson annulation sequence has been developed for asymmetric synthesis of 6-fluoroyclohex-2-en-1-ones and 4,6-difluorocyclohex-2-en-1-ones. The reactions promoted by cinchona alkaloid amine afforded products bearing two or three stereocenters in good to excellent yields with up to 99% ee and 20:1 dr.
A Pd-Catalyzed [4 + 2] Annulation Approach to Fluorinated N-Heterocycles
García-Vázquez, Víctor,Hoteite, Larry,Lakeland, Christopher P.,Watson, David W.,Harrity, Joseph P. A.
supporting information, p. 2811 - 2815 (2021/05/05)
3-Fluoro- and trifluoromethylthio-piperidines represent important building blocks for discovery chemistry. We report a simple and efficient method to access analogs of these compounds that are armed with rich functionality allowing them to be chemoselectively derivatized with high diastereocontrol.
Recyclable Organocatalysts for a One-Pot Asymmetric Synthesis of 2-Fluorocyclohexanols Bearing Six Contiguous Stereocenters
Huang, Xin,Liu, Miao,Jasinski, Jerry P.,Peng, Bo,Zhang, Wei
, p. 1919 - 1926 (2017/06/09)
A recyclable fluorous bifunctional Cinchona alkaloid/thiourea-catalyzed quadruple fluorination/Michael/Michael/aldol sequence has been developed for the one-pot synthesis of cyclohexanols bearing six contiguous stereocenters including a fluorinated tertiary carbon. By using readily available starting materials including β-keto esters, β-nitrostyrenes, and α,β-unsaturated aldehydes, fully functionalized cyclohexanols were synthesized in 52–80% yields with up to 99% ee and >20:1 dr. The fluorous catalyst could be easily recovered by fluorous solid-phase extraction in 94–97% yield and >98% purity. In addition to the high synthetic efficiency achieved through the pot economic reactions, other green techniques such as transition metal-free catalysis and catalyst recovery are also employed. (Figure presented.).
