A new synthesis of α-fluorovinylsulfones utilizing the Peterson olefination methodology

Transformations of Organic Molecules with F-TEDA-BF4 in Ionic Liquid Media

“…After the reaction had ceased, the products were extracted with t -BuOMe (4x2 mL), the combined organic phase was washed with water and after drying of the organic phase over anhydrous Na 2 SO 4 , the insoluble material was filtered off, while the reaction mixture was concentrated in vacuo . The crude reaction mixture was analyzed by TLC, 1 H-NMR, 19 F-NMR and MS and the products identified on the basis of comparison of their spectroscopic data with literature values [ 27 , 28 , 29 , 30 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 ].…”

Designer HF-Based Fluorination Reagent: Highly Regioselective Synthesis of Fluoroalkenes and gem-Difluoromethylene Compounds from Alkynes

“… 9 Typical synthetic methods of fluoroalkenes include tandem addition–reduction, 9a tandem addition–elimination, 10 Shapiro reaction, 7b Julia–Kocienski olefination, 11 and Peterson olefination. 12 Sadighi and co-workers have reported a SIPr–Au catalyzed monohydrofluorination of alkynes using Et 3 N/HF, 13 but because of the low acidity of the Et 3 N/HF system, stoichiometric amounts of acid and acidic cocatalyst have to be used. Also, this method works only for internal alkynes, where there is no reliable way to control the regioselectivity.…”

Julia Olefination as a General Route to Phenyl (α-Fluoro)vinyl Sulfones

“…The observed stereoselectivities in these cases can be rationalized on the same principles as described in our synthesis of afluoroacrylates. 13b The stereochemical outcome in reactions with aldehydes using our methodology is complementary to other known methods, where the major or exclusive isomer formed was E. 3,7,19 In the case of aromatic aldehydes stereoselectivity decreased with the bulk of the aldehyde (entries 6, 8), however, branching of the aldehyde did not appear to have any influence on the E/Z ratio in the case of aliphatic aldehydes (entries 10-12).…”

“…Also, vinyl sulfones can be used for cycloadditions and are Michael acceptors. 3b,6 (a-Fluoro)vinyl sulfones can be prepared by various approaches, such as: addition of fluoromethyl phenyl sulfone anion to carbonyl compounds, 3a Horner-Wadsworth-Emmons 3-5 or Peterson's olefination, 7 syn elimination of sulfoxides, 8 or via electrochemical method. 9 Synthesis of vinyl fluorides using fluorobis(phenylsulfonyl)methane has also been shown.…”