Synthesis of 4-nitrophenyl sulfones and application in the modified Julia olefination

4-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)]


Published in:
Synlett, 8, 1255-1259
Year:
2006
Keywords:
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 (stereoselective ; Julia 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 oxidn
Note:
CAN 145:210697
25-9
Benzene, Its Derivatives, and Condensed Benzenoid Compounds
Institut de Chimie des Substances Naturelles,CNRS,Gif-sur-Yvette,Fr.
Journal
0936-5214
written in English.
70-34-8 (1-Fluoro-2,4-dinitrobenzene); 86-81-7 (3,4,5-Trimethoxybenzaldehyde); 99-61-6 (3-Nitrobenzaldehyde); 100-10-7 (4-Dimethylaminobenzaldehyde); 100-52-7 (Benzaldehyde); 100-53-8 (Benzylthiol); 104-55-2 (Cinnamaldehyde); 104-88-1 (4-Chlorobenzaldehyde); 111-31-9 (1-Hexanethiol); 120-14-9 (3,4-Dimethoxybenzaldehyde); 123-11-5 (4-Methoxybenzaldehyde); 350-46-9 (1-Fluoro-4-nitrobenzene); 529-20-4 (2-Methylbenzaldehyde); 552-89-6 (2-Nitrobenzaldehyde); 555-16-8 (4-Nitrobenzaldehyde); 623-51-8 (Ethyl mercaptoacetate); 830-79-5 (2,4,6-Trimethoxybenzaldehyde); 1122-91-4 (4-Bromobenzaldehyde); 6361-21-3 (2-Chloro-5-nitrobenzaldehyde); 7311-34-4 (3,5-Dimethoxybenzaldehyde) Role: RCT (Reactant), RACT (Reactant or reagent) (prepn. and modified stereoselective Julia olefination of nitrophenyl sulfones); 15863-52-2P; 39180-20-6P; 42497-88-1P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and modified stereoselective Julia olefination of nitrophenyl sulfones); 103-30-0P; 838-95-9P; 846-15-1P; 886-65-7P; 1657-50-7P; 1694-19-5P; 1694-20-8P; 3892-92-0P; 4714-25-4P; 4714-26-5P; 10201-58-8P; 13041-70-8P; 21956-56-9P; 22257-16-5P; 22887-34-9P; 24393-52-0P; 24393-53-1P; 24393-56-4P; 24393-61-1P; 74809-43-1P; 135987-61-0P; 171569-32-7P; 337365-52-3P; 353801-06-6P; 847610-45-1P; 866934-79-4P; 904925-42-4P; 904925-43-5P; 904925-44-6P; 904925-45-7P; 904925-46-8P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. and modified stereoselective Julia olefination of nitrophenyl sulfones)
Laboratories:




 Record created 2010-11-25, last modified 2018-12-03


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