61476-94-6Relevant academic research and scientific papers
Direct Synthesis of γ-Keto Sulfones from Allylic Alcohols: One-Pot Palladium(II)-Catalyzed Generation of Enones Followed by Water-Mediated 1,4-Addition of Organosulfinates
Vellakkaran, Mari,Andappan, Murugaiah M. S.,Nagaiah, Kommu,Nanubolu, Jagadeesh Babu
supporting information, p. 3575 - 3583 (2016/07/28)
Allylic alcohols were exploited as synthetic precursors of γ-keto sulfones. The reaction involved the one-pot generation of α,β-enones in situ from the allylic alcohols by using a PdII–dioxygen catalytic system and subsequent sulfa-Michael addition in the presence of water. Importantly, water was identified as a sustainable substitute for a toxic copper salt to promote organosulfonyl addition. Diverse examples of aromatic and aliphatic γ-keto sulfones were prepared. Specially, Ar–X (X = Br, Cl) bonds were tolerated, which indicated a chemoselective catalytic system for the preparation of halogen-bearing γ-keto sulfones. This one-pot method does not require an acid, a base, or isolation of any intermediate. Control experiments indicated that the active catalyst of the first step also promoted the subsequent C–S bond-formation reaction. Water was found to accelerate the reaction rate and to be involved in the protonolysis of the σ-alkylpalladium complex, as corroborated by deuterium incorporation.
Studies on the synthesis, stability and conformation of 2-sulfonyl-oxetane fragments
Morgan,Hollingsworth,Bull
, p. 5265 - 5272 (2015/05/13)
2-(Arylsulfonyl)oxetanes have been prepared as new structural motifs of interest for medicinal chemistry. These are designed to fit within fragment space and be suitable for screening in fragment based drug discovery, as well as being suitable for further elaboration or incorporation into drug-like compounds. The oxetane ring is constructed through an efficient C-C bond forming cyclisation which allows the incorporation of a wide range of aryl-sulfonyl groups. Furthermore, biaryl-containing compounds can be accessed through Suzuki-Miyaura coupling from halogenated derivatives. With a number of oxetane containing fragment compounds available, their pH stability was assessed, indicating good half-life values for mono-substituted aryl sulfonyl oxetanes across the pH range (1 to 10). Solubility and metabolic stability data is also reported. Finally, the conformation of the fragments is assessed computationally, providing an indication of possible binding orientations.
FeCl3ATMSCl: An effective catalytic system for the conjugate addition of sodium p-toluenesulfinate to αβ-enones
Sreedhar,Reddy, M. Amamath,Reddy, P. Surendra
experimental part, p. 1949 - 1952 (2009/04/10)
A new protocol for the β-sulfonation of αβ-unsaturated carbonyl compounds is described. The method employs FeCl3 as catalyst and TMSC1 as additive for conjugate addition of sodiump-toluenesulfinate to enones.
4-[(4-methylphenyl)sulfonyl]-1-(triphenylphosphoranylidene)-2- butanone and its dianion as versatile tools in organic synthesis
Barco, Achille,Benetti, Simonetta,De Risi, Carmela,Marchetti, Paolo,Pollini, Gian P.,Zanirato, Vinicio
, p. 1973 - 1976 (2007/10/03)
The title compound and the corresponding dianion have been used as convenient precursors for substituted divinyl ketones in both carbo- and heterocyclization reactions in a one-pot three-step sequence leading to substituted carbo- and heterocyclic ring systems and for the construction of the 4-keto-2-alkenoate subunit, a common structural feature of a variety of natural compounds, respectively.
Lithiated 3-Tosylpropanal and 4-Tosyl-2-butanone Dimethyl Acetals as β-Acylvinyl Anion Equivalents for the Synthesis of Unsaturated 1,4-Dicarbonyl Compound and α,β-Butenolides
Bonete, Pedro,Najera, Carmen
, p. 2763 - 2776 (2007/10/02)
The lithiation of 1,1-dimethoxy-3-tosyllpropane (7a) and 2,2-dimethoxy-4-tosylbutane (7b) followed by reaction with acyl chlorides affords, after p-toluenesulfinic acid elimination, ene-1,4-dicarbonyl compounds in a stereoselective manner.In the case of compound 7a, derived from acrolein, sequential monolithiation and reaction with carbonyl compounds give cyclic acetals, which after oxidation and elimination of p-toluenesulfinic acid are transformed into α,β-butenolides.
"Syn-Effect" in the Conversion of (E)-Vinylic Sulfones to the Corresponding Allylic Sulfones
Hirata, Takaki,Sasada, Yoshihiro,Ohtani, Takashi,Asada, Takahiro,Kinoshita, Hideki,et al.
, p. 75 - 96 (2007/10/02)
It was found that (E)-vinylic sulfones preferentially afford (Z)-allylic sulfones as kinetically-controlled products by treatment with a base under mild conditions, while (Z)-vinylic sulfones give (E)-allylic sulfones.Such stereochemical relationship was
REACTIONS OF ARYLAZO ARYL SULFONES WITH α,β-UNSATURATED ESTERS AND KETONES CATALYZED BY PALLADIUM(0) COMPLEX
Kamigata, Nobumasa,Satoh, Akira,Yoshida, Masato
, p. 121 - 130 (2007/10/02)
The palladium(0) catalyzed reactions of arylazo aryl sulfones (1) with α,β-unsaturated esters in benzene give aryl-substituted esters as major products and hydroarylated esters as minor products.The reactions of 1 with acyclic α,β-unsaturated ketones give considerable amounts of hydroarylated ketones and aryl-substituted ketones under similar conditions, whereas the reactions of 1 with cyclic α,β-unsaturated ketones afforded selectively hydroarylated compounds and no formation of aryl-substituted ketones was found.A plausible reaction mechanism is proposed.Key words: Arylazo aryl sulfones; palladium(0) catalyst; arylation; α,β-unsaturated carbonyl compounds; diarylpalladiumII) intermediate; catalytic cycle.
SULFONE MEDIATED RUPE AND RAPHAEL REARRANGEMENTS
Barre, V.,Massias, F.,Uguen, D.
, p. 7389 - 7392 (2007/10/02)
Base-catalysed addition of methanol to propargylic sulfones selectively gave β-ketosulfones whereas mercuric salts catalysed additions gave γ-ketosulfones.The latter process has been used to prepare one half of pyrenophorine.
