676486-18-3Relevant academic research and scientific papers
Metal-Free Chemoselective Reaction of Sulfoxonium Ylides and Thiosulfonates: Diverse Synthesis of 1,4-Diketones, Aryl Sulfursulfoxonium Ylides, and β-Keto Thiosulfones Derivatives
Wang, Fei,Liu, Bo-Xi,Rao, Weidong,Wang, Shun-Yi
supporting information, p. 6600 - 6604 (2020/09/02)
A diverse chemoselective insertion reaction of sulfoxonium ylides and thiosulfonates under transition-metal-free conditions is developed, which successfully affords 1,4-diketone compounds, arylthiosulfoxide-ylides, and β-keto thiosulfones, respectively. The nucleophilic addition of two molecular sulfoxonium ylides to construct sulfone-substituted 1,4-dione compounds is the highlight of this work.
Rhodium(III)-catalyzed C–H functionalization of C-alkenyl azoles with sulfoxonium ylides for the synthesis of bridgehead N-fused [5,6]-bicyclic heterocycles
Hoang, Gia L.,Ellman, Jonathan A.
, p. 3318 - 3324 (2021/05/17)
The synthesis of bridgehead N-fused [5,6]-bicyclic heterocycles via rhodium(III)-catalyzed C–H functionalization of C-alkenyl azoles with sulfoxonium ylides is disclosed. Reactions proceeded in good to high yields for a range of aryl, heteroaryl and alkyl sulfoxonium ylides. In addition, 2-alkenyl imidazoles with different substitution patterns as well as C-alkenyl triazoles were effective inputs. The reaction could also be performed under straightforward bench top conditions.
Catalyst-Free Insertion of Sulfoxonium Ylides into Aryl Thiols. A Direct Preparation of β-Keto Thioethers
Dias, Rafael M. P.,Burtoloso, Antonio C. B.
supporting information, p. 3034 - 3037 (2016/07/06)
Insertion of sulfoxonium ylides into the S-H bond of aryl thiols without the need for a catalyst is demonstrated, furnishing β-keto thioethers in excellent yield in most cases. The method overcomes traditional syntheses that employ metal catalysts in combination with diazo compounds or toxic and hard-prepared haloketones. The experimental setup consists of mixing the reagents in acetonitrile at room temperature. Additional experimental as well as kinetic isotopic effect studies give some insight into the mechanism of this reaction.
Improvement in the one-carbon chain extension of esters with dimethylsulfoxonium methylide
Luong, Hoa,Luss-Lusis, Eduard,Tanoury, Gerald J.,Nugent, William A.
, p. 4238 - 4241 (2013/07/26)
A recent report suggests that the reaction of dimethylsulfoxonium methylide with esters does not produce a chain-extended sulfur ylide as previously reported, but rather affords the corresponding carboxylate salt. We have investigated this assertion by using a combination of ab initio molecular orbital calculations, spiking studies, and isotopic labeling. The formation of carboxylate is unambiguously demonstrated to arise through hydrolysis involving adventitious water, principally derived from moisture in commercial trimethylsulfoxonium chloride. Careful vacuum drying of this reagent diminishes the competing hydrolytic pathway resulting in higher yields for the chain-extension reaction than previously reported. Copyright
Unusual reactivity of dimethylsulfoxonium methylide with esters
Leggio, Antonella,De Marco, Rosaria,Perri, Francesca,Spinella, Mariagiovanna,Liguori, Angelo
scheme or table, p. 114 - 118 (2012/02/14)
The dimethylsulfoxonium methylide was treated with esters under mild conditions to rapidly afford the corresponding carboxylic acids at room temperature. Moreover, by performing the procedure on enantiopure substrates, it was demonstrated that the reaction occurs without racemization. 18O-labeled reagents showed that the reaction does not proceed through an ester hydrolysis mechanism. The reactions are characterized by an unusual reactivity of the dimethylsulfoxonium methylide. This methodology is general and can be considered a valid alternate route for ester cleavage when a substrate is sensitive to hydrolysis conditions.
PROCESS FOR THE PREPARATION OF ALPHA-CHLOROKETONES FROM ALKYL ESTERS
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Page/Page column 4, (2010/02/11)
The present invention relates to a process for the preparation of α-chloroketones from readily available alkyl esters by the reaction of a sulfoxonium ylide on said alkyl esters to generate a keto sulfoxonium ylide that is in turn treated with anhydrous HCl.
One-Carbon Chain Extension of Esters to α-Chloroketones: A Safer Route without Diazomethane
Wang, Dengjin,Schwinden, Mark D.,Radesca, Lilian,Patel, Bharat,Kronenthal, David,Huang, Ming-Hsing,Nugent, William A.
, p. 1629 - 1633 (2007/10/03)
The reaction of a variety of methyl esters with dimethylsulfoxonium methylide at 0-25 °C affords the chain-extended β-keto dimethylsulfoxonium ylides. Subsequent treatment with hydrogen chloride in THF proceeds with loss of DMSO to afford the corresponding α-chloroketones. This sequence has been utilized to convert the methyl esters of CBZ-protected alanine and valine to the anti N-protected α-amino epoxides, which are important pharmaceutical intermediates. When the same protocol is applied to BOC-protected phenylalanine methyl ester, epimerization occurs so that the use of a more reactive aryl ester is required. This chemistry provides a practical route to α-chloroketones that avoids the use of toxic and explosive diazomethane.
