Reaction of Baylis–Hillman Adducts with Fluorinated Silanes

Abstract

In Wasser geht es besser: In situ erzeugte [Ru(O2CR)2(Aren)]‐Katalysatoren vermitteln eine effiziente direkte ortho‐Arylierung funktionalisierter Arene mit Chlorarenen oder Chlorheterocyclen in Wasser (siehe Schema; KOPiv=Kaliumpivalat), ohne dass ein Tensid benötigt wird. Die Aktivität dieser Katalysatoren ist in Wasser höher als in organischen Lösungsmitteln.

Reactions of fluorinated silanes with 2-nitrocinnamates

“…occurs rapidly and exothermically, but affords the product 2a in only 70% yield. However, decreasing the reaction temperature significantly slowed down the process (entries [8][9][10][11]. Finally, the best result was obtained when reaction was performed in dichloromethane at À20 8C furnishing 2a in 82% isolated yield (entry 12).…”

“…We also showed that a,b-unsaturated nitriles, esters and ketones containing additional activating acetoxy group (acylated Baylis-Hillman adducts) can be pentafluorophenylated with the use of complicated silanes Me n Si(C 6 F 5 ) 4Àn [8]. In continuation of these studies, herein we report the reactions of trimethylsilicon reagents Me 3 SiR f with 2-nitrocinnamates.…”

“…The interaction of silanes with C5 5O and C5 5N bonds is very well developed [1], whereas addition of fluorinated group to C5 5C bond still has a limited scope [4][5][6][7][8].…”

Nucleophilic trifluoromethylation of carbonyl compounds and derivatives

“…51 However, an inseparable mixture of Michael addition product 78 and derivative 79 (both as isomeric mixtures) was obtained with low yield (30%).…”

Regioselective 1,4-trifluoromethylation of α,β-unsaturated ketones via a S-(trifluoromethyl)diphenylsulfonium salts/copper system

“…The nucleophilic trifluoromethylation to conjugated alkenes essentially occurs solely via a 1,2-addition [1–11], not a 1,4-addition (Scheme 1), with the exception of non-general examples of 1,4-additive trifluoromethylation of (trifluoromethyl)trimethylsilane (Me 3 SiCF 3 , Ruppert–Prakash reagent) to very specific substrates such as trans -1-benzoyl-2-(dimethylamino)ethylene [12], 2-polyfluoroalkylchromones [13–14], isoxazoles with a nitro group at the 4-position [15], and Morita–Baylis–Hillman adducts (via S N 2’ [16] or successive S N 2’/S N 2’ mode [17]).…”