Mirk, DanielaGrassot, Jean-MarieZhu, Jieping2010-11-252010-11-252010-11-25200610.1055/s-2006-939682https://infoscience.epfl.ch/handle/20.500.14299/584434-Nitrophenyl (NP) sulfones were successfully employed in the modified Julia olefination reaction with carbonyl compds. The olefination reaction proceeds through a sequence of aldol addn., Smiles rearrangement, and elimination. The sulfones are easily prepd. in high yields in a two-step sequence starting from inexpensive com. available para-fluoronitrobenzenes via nucleophilic arom. substitution by a mercaptan and subsequent oxidn. under std. conditions. The modified Julia reaction between NP sulfones and a wide variety of arom. aldehydes affords the corresponding styrenes, stilbenes, and cinnamate derivs. in yields ?97% and good stereoselectivities. A mechanistic rationale is advanced to explain the obsd. results. [on SciFinder (R)]Rearrangement (Smiles; modified stereoselective Julia olefination of nitrophenyl sulfones); Aldehydes Role: RCT (Reactant)RACT (Reactant or reagent) (arom.; prepn. and modified stereoselective Julia olefination of nitrophenyl sulfones); Substitution reaction (arom.; prepn. of nitrophenyl sulfones by nucleophilic arom. substitution of fluoronitrobenzene with mercaptane); Aromatic hydrocarbons Role: SPN (Synthetic preparation)PREP (Preparation) (aryl alkenes; prepn. and modified stereoselective Julia olefination of nitrophenyl sulfones); Sulfones Role: RCT (Reactant)SPN (Synthetic preparation)PREP (Preparation)RACT (Reactant or reagent) (aryl; prepn. and modified stereoselective Julia olefination of nitrophenyl sulfones); Alkenes Role: SPN (Synthetic preparation)PREP (Preparation) (aryl; prepn. and modified stereoselective Julia olefination of nitrophenyl sulfones); Stereochemistry (modified stereoselective Julia olefination of nitrophenyl sulfones); Thiols Role: RCT (Reactant)RACT (Reactant or reagent) (prepn. of nitrophenyl sulfones by nucleophilic arom. substitution of fluoronitrobenzene with mercaptane); Olefination (stereoselectiveJulia olefination; prepn. and modified stereoselective Julia olefination of nitrophenyl sulfones); Aromatic compounds Role: RCT (Reactant)SPN (Synthetic preparation)PREP (Preparation)RACT (Reactant or reagent) (sulfones; prepn. and modified stereoselective Julia olefination of nitrophenyl sulfones)nitrophenyl sulfone prepn stereoselective Julia olefination; arom aldehyde nitrophenyl sulfone stereoselective Julia olefination; aryl alkene stereoselective prepn; fluoronitrobenzene mercaptane nucleophilic arom substitution oxidntext::journal::journal article::research article